Microfibrillated cellulose with enhanced properties and methods of making the same

ABSTRACT

Methods of re-dispersing and de-agglomerating dewatered, partially dried and dried compositions of microfibrillated cellulose and compositions of microfibrillated cellulose and inorganic particulate material, into liquid compositions comprising same, by applying ultrasonic energy to such liquid compositions of dewatered, partially dried and dried compositions of microfibrillated cellulose, or compositions of microfibrillated cellulose and inorganic particulate material. Methods for preparing an aqueous suspension comprising microfibrillated cellulose and, optionally, inorganic particulate material, with enhanced viscosity and tensile strength properties, suitable for use in methods of making paper or coating paper, and to filled and coated papers made from such aqueous suspensions.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a U.S. National Stage entry application of PCTInternational Application No. PCT/IB2018/000518, filed Apr. 20, 2018,which claims priority to U.S. Provisional No. 62/488,299, filed Apr. 21,2017, the entire contents of which is incorporated herein by reference.

FIELD OF THE INVENTION

The present invention relates to methods of re-dispersing andde-agglomerating dewatered, partially dried and dried compositions ofmicrofibrillated cellulose, as well as compositions of microfibrillatedcellulose and inorganic particulate material, into liquid compositionscomprising same, by applying ultrasonic energy to such liquidcompositions of dewatered, partially dried and dried compositions ofmicrofibrillated cellulose, or compositions of microfibrillatedcellulose and inorganic particulate material. The present invention alsorelates to preparing an aqueous suspension comprising microfibrillatedcellulose and, optionally, inorganic particulate material, with enhancedviscosity and tensile strength properties, suitable for use in methodsof making paper or coating paper, and to filled and coated papers madefrom such aqueous suspensions.

BACKGROUND OF THE INVENTION

Microfibrillated cellulose and, optionally, inorganic particulatematerials, for example an alkaline earth metal carbonate (e.g., calciumcarbonate) or kaolin, are used widely in a number of applications. Theseinclude the production of microfibrillated cellulose and, optionally,mineral containing compositions, which may be used as fillers in papermanufacture and/or in paper coatings. In paper and coated paperproducts, such fillers are typically added to replace a portion of othermore expensive components of the paper and/or coated paper product.Fillers may also be added with an aim of modifying the physical,mechanical, and/or optical requirements of paper and/or coated paperproducts. Clearly, the greater the amount of filler that can beincluded, the greater potential for cost savings. However, the amount offiller added and the associated cost saving must be balanced against thephysical, mechanical and optical requirements of the final paper productor coated paper product. Thus, there is a continuing need for thedevelopment of improved fillers for paper and paper coatings, which canbe used at a high loading level without adversely affecting thephysical, mechanical and/or optical requirements of such paper and/orcoated paper products. There is also a need for the development ofmethods for preparing such fillers economically.

The present invention seeks to provide alternative and/or improvedfillers for paper and/or coated paper products which may be incorporatedin the paper and/or coated paper product at relatively high loadinglevels, whilst maintaining or even improving the physical, mechanicaland/or optical properties of the paper and/or coated paper product. Thepresent invention also seeks to provide an economical method forpreparing such fillers. As such, the present inventors have surprisinglyfound that a filler comprising microfibrillated cellulose and,optionally, an inorganic particulate material, can be prepared byeconomical methods and can be loaded in paper products and/or coatedpaper products at relatively high levels, whilst maintaining or evenimproving the physical, mechanical and/or optical properties of thefinal paper product. The application of ultrasonic energy to asuspension of microfibrillated cellulose, or microfibrillated cellulosesuspensions comprising at least one inorganic particulate material hassurprisingly been found to efficiently produce such suspensions havingimproved tensile strength and/or enhanced viscosity properties.

Further, the present invention seeks to address the problem of preparingmicrofibrillated cellulose and microfibrillated cellulose and inorganicparticulate material compositions economically on an industrial scale.Current methods of microfibrillating cellulosic material andmicrofibrillated cellulose and inorganic particulate material requirerelatively high amounts of energy, owing in part to the relatively highviscosity of the starting material and the microfibrillated-containingproduct, and a commercially viable process for preparingmicrofibrillated cellulose on an industrial scale has hitherto beforeproved elusive.

Additionally, the present invention seeks to address the problem ofre-dispersing dewatered, partially dried or essentially driedmicrofibrillated cellulose compositions or microfibrillated celluloseand inorganic particulate matter compositions in a liquid medium,optionally in the presence of an additive other than inorganicparticulate material and/or in the presence of a combination ofinorganic particulate materials. The additive and/or combination ofinorganic particulate materials may, for example, enhance a mechanicaland/or physical property of the re-dispersed microfibrillated celluloseor microfibrillated cellulose and inorganic particulate materialcomposition. The present invention further relates to compositionscomprising re-dispersed microfibrillated cellulose and, optionally,inorganic particulate material and the use of re-dispersedmicrofibrillated cellulose and, optionally, inorganic particulatematerial, in an article, product or composition. The solution to theproblem is to apply ultrasonic energy in the re-dispersion ofcompositions of microfibrillated cellulose or compositions ofmicrofibrillated cellulose and at least one inorganic particulatematerial as herein described.

SUMMARY OF THE INVENTION

According to a first aspect, the present invention is directed to amethod for re-dispersing dewatered, partially dried or essentially driedmicrofibrillated cellulose, the method comprising the steps of:

-   -   (a) adding a quantity of a suitable dispersing liquid (e.g.,        water) to a tank having at least one inlet and an outlet,        wherein the tank further comprises a mixer and a pump attached        to the outlet;    -   (b) adding a quantity of dewatered, partially dried or        essentially dried microfibrillated cellulose to the tank through        the at least one inlet in sufficient quantity to yield a liquid        composition of microfibrillated cellulose at a desired solids        concentration;    -   (c) mixing the dispersing liquid and the dewatered, partially        dried or essentially dried microfibrillated cellulose in the        tank with the mixer to partially de-agglomerate and re-disperse        the microfibrillated cellulose to form a flowable slurry;    -   (d) pumping the flowable slurry with the pump to an inlet of a        flow cell, wherein the flow cell comprises one or more        sonication probe in series and at least one outlet;    -   (e) applying ultrasonic energy to the slurry of at least 200        kWh/t continuously by the sonication probe at a frequency range        of 19 to 100 kHz;    -   (f) collecting the re-dispersed suspension comprising        microfibrillated cellulose with enhanced tensile strength and/or        viscosity properties from the at least one outlet of the flow        cell in a suitable holding vessel.

According to a second aspect, the present invention, is directed to amethod for re-dispersing dewatered, partially dried or essentially driedmicrofibrillated cellulose, the method comprising the steps of:

-   -   (a) adding a quantity of a suitable dispersing liquid to a tank        having at least one inlet and an outlet, wherein the tank        further comprises a mixer and a pump attached to the outlet;    -   (b) adding a quantity of dewatered, partially dried or        essentially dried microfibrillated cellulose to the tank through        the at least one inlet in sufficient quantity to yield a liquid        composition of microfibrillated cellulose at a desired solids        concentration;    -   (c) mixing the dispersing liquid and the dewatered, partially        dried or essentially dried microfibrillated cellulose in the        tank with the mixer to partially de-agglomerate and re-disperse        the microfibrillated cellulose to form a flowable slurry;    -   (d) pumping the flowable slurry with the pump to an inlet of a        flow cell, wherein the flow cell comprises one or more        sonication probe in series and a first outlet; and wherein a        second outlet of the flow cell is connected to a second inlet of        the tank, thereby providing for a continuous recirculation loop        providing for the continuous application of ultrasonic energy to        the slurry for a desired time period and/or total energy input        range;    -   (e) applying ultrasonic energy to the slurry of at least 200        kWh/t continuously by the sonication probe at a frequency range        of 19 to 100 kHz;    -   (f) collecting the re-dispersed suspension comprising        microfibrillated cellulose with enhanced tensile strength and/or        viscosity properties from the first outlet of the flow cell in a        suitable holding vessel.

According to a third aspect, the present invention is directed toprocesses of the first and second aspects, wherein the dewatered,partially dried or essentially dried microfibrillated cellulosecomposition further comprises at least one inorganic particulatematerial.

In an embodiment of the first, second or third aspect of the presentinvention the cumulative ultrasonic energy input may be from about 1,000kWh/t to about 10,000 kWh/t or between about 1,000 kWh/t and about 2,000kWh/t, or about 2,000 kWh/t to about 3,000 kWh/t.

In an embodiment of the first, second or third aspect of the presentinvention the flow cell comprises a cooling jacket for maintaining atemperature of the suspension of microfibrillated cellulose in the rangeof about 1° C. to about 80° C., or from about 20° C. to about 50° C., orat room temperature, or about 20° C.

In an embodiment of the first, second or third aspect of the presentinvention the flow cell comprises an adjustable valve at the secondoutlet to create back pressure of the recirculated liquid of from about0 to about 10 bar, or from about 0 to about 4 bar, preferably about 3bar.

In an embodiment of the first, second or third aspect of the presentinvention, the flow cell further comprises one or more boosters tomechanically increase or decrease the amplitude of the at least onesonication probe.

In an embodiment of the first and second aspect of the presentinvention, the liquid composition of microfibrillated cellulose is about0.5% to about 10%, or about 0.5% to 5% fibre solids, and in anembodiment of the third aspect, the liquid composition ofmicrofibrillated cellulose and inorganic particulate material is about0.5% to about 10%, or about 0.5% to 5% fibre solids.

In an embodiment of the first, second and third aspects of the presentinvention, the ultrasonic energy is applied for about 1 to about 120minutes, or about 1 to about 90 minutes, or about 1 to about 75 minutes,or about 1 to about 60 minutes, or about 1 to about 45 minutes or about1 to about 30 minutes.

In an embodiment of the first and second aspect of the presentinvention, the microfibrillated cellulose may be pelletized, and in thethird aspect, microfibrillated cellulose and inorganic particulatematerial may be pelletized.

In an embodiment of the first, second and third aspects of the presentinvention, the ultrasonic energy may be applied until a specifiedcumulative energy input is achieved. In additional embodiments, thecumulative energy input may be greater than 200 kWh/t, greater than 400kWh/t, or greater than 500 kWh/t, or greater than 1,000 kWh/t, orgreater than 1,500 kWh/t, or greater than 2,000 kWh/t, or greater than2,500 kWh/t, or greater than 3,000 kWh/t, or greater than 4,000 kWh/t,or greater than 5,000 kWh/t, or greater than 6,000 kWh/t, or greaterthan 7,000 kWh/t, or between 200 kWh/t and 10,000 kWh/t., or about 200kWh/t and 5,000 kWh/t, or about 200 kWh/t and 4,000 kWh/t, or about 200kWh/t and 3,000 kWh/t, or about 200 kWh/t and 2,000 kWh/t.

In an embodiment of the second and third aspects of the presentinvention, the recirculation loop may comprise a high shear mixer.

In an embodiment of the first, second and third aspects of the presentinvention, the FLT index for the suspension of microfibrillatedcellulose and the suspension of the microfibrillated cellulose andinorganic particulate material may reach 7.5 Nm/g or more, 7.5 Nm/g ormore, 8 Nm/g or more, 8.5 Nm/g or more, 9 Nm/g or more, 9.5 Nm/g ormore, 10 Nm/g or more, 10.5 Nm/g or more, 11 Nm/g or more, 11.5 Nm/g ormore, 12 Nm/g or more, 12.5 Nm/g or more, 13 Nm/g or more, 13.5 Nm/g ormore, 14 Nm/g or more, 14.5 Nm/g or more, or 15 Nm/g or more, throughthe methods disclosed in the specification.

In an embodiment of the first, second and third aspects of the presentinvention, the FLT index may be improved by about 5%, about 6%, about7%, about 7.5%, about 8%, about 9%, about 10%, about 12.5%, about 15% orabout 20%, or more, compared to suspensions of microfibrillatedcellulose or microfibrillated cellulose and inorganic particulatematerial produced without the application of ultrasonic energy treatmentto the slurry or suspension.

In an embodiment of the first, second and third aspects of the presentinvention, viscosity may be improved by about 5%, about 6%, about 7%,about 7.5%, about 8%, about 9%, about 10%, about 12.5%, about 15% orabout 20%, or more, compared to suspensions of microfibrillatedcellulose or microfibrillated cellulose and inorganic particulatematerial produced without the application of ultrasonic energy treatmentto the slurry or suspension.

In embodiments of the first, second and third aspects of the presentinvention, the microfibrillated cellulose may be prepared from achemical pulp, or a chemithermomechanical pulp, or a mechanical pulp, ora recycled pulp, or a paper broke pulp, or a papermill waste stream, orwaste from a papermill, or combinations thereof.

In embodiments of the third aspect of the present invention, theinorganic particulate material may comprise alkaline earth metalcarbonate or sulphate, such as calcium carbonate, magnesium carbonate,dolomite, gypsum, a hydrous kandite clay such as kaolin, halloysite orball clay, an anhydrous (calcined) kandite clay such as metakaolin orfully calcined kaolin, talc, mica, perlite or diatomaceous earth, orcombinations thereof. In certain embodiments, calcium carbonate and/orkaolin are particularly preferred.

In embodiments of the first and second aspects of the present invention,the suspensions of microfibrillated cellulose, or with enhancedviscosity and tensile strength properties obtained by the method aresuitable for use in a method of making paper or coating paper, paintsand coatings, inks, oilfield chemicals, composites, consumer products,cosmetic products, pharmacological products and food product.

In embodiments of the third aspect of the present invention thesuspensions of microfibrillated cellulose and inorganic particulatematerial with enhanced viscosity and tensile strength propertiesobtained by the method are suitable for use in a method of making paperor coating paper, paints and coatings, inks, oilfield chemicals,composites, consumer products, cosmetic products, pharmacologicalproducts and food product.

According to a fourth aspect, the present invention is directed to amethod for re-dispersing dewatered, partially dried or essentially driedmicrofibrillated cellulose, the method comprising the steps of:

-   -   (a) adding a quantity of a suitable dispersing liquid (e.g.,        water) to a closed tank, wherein the tank comprises an inlet and        an outlet connected to a pump comprising a first inlet and a        first outlet, and a flow cell comprising a second inlet and a        second outlet, and further comprising at least one sonication        probe, thereby forming a closed recirculation loop;    -   (b) adding a quantity of dewatered, partially dried or        essentially dried microfibrillated cellulose to the tank in        sufficient quantity to yield a liquid composition of        microfibrillated cellulose at a desired solids concentration;    -   wherein the liquid composition comprising microfibrillated        cellulose of step (b) is continuously recirculated through the        recirculation loop;    -   (c) applying ultrasonic energy of at least 200 kWh/t        intermittently or continuously by the sonication probe at a        frequency range of 20 to 100 Hz to the liquid composition of        microfibrillated cellulose,

thereby forming a re-dispersed suspension comprising microfibrillatedcellulose with tensile strength and/or viscosity properties.

According to a fifth aspect, the present invention is directed to amethod for re-dispersing dewatered, partially dried or essentially driedmicrofibrillated cellulose and inorganic particulate material, themethod comprising the steps of:

-   -   (a) adding a quantity of a suitable dispersing liquid (e.g.,        water) to a closed tank, wherein the tank comprises an inlet and        an outlet connected to a pump comprising a first inlet and a        first outlet, and a flow cell comprising a second inlet and a        second outlet, and further comprising at least one sonication        probe, thereby forming a closed recirculation loop;    -   (b) adding a quantity of dewatered, partially dried or        essentially dried microfibrillated cellulose and inorganic        particulate material to the tank in sufficient quantity to yield        a liquid composition of microfibrillated cellulose at a desired        solids concentration;    -   wherein the liquid composition comprising microfibrillated        cellulose and inorganic particulate material of step (b) is        continuously recirculated through the recirculation loop;    -   (c) applying ultrasonic energy of at least 200 kWh/t        intermittently or continuously by the sonication probe at a        frequency range of 20 to 100 Hz to the liquid composition of        microfibrillated cellulose and inorganic particulate material,

thereby forming a re-dispersed suspension comprising microfibrillatedcellulose and inorganic particulate material with tensile strengthand/or viscosity properties.

In an embodiment of the fourth or fifth aspect of the present invention,the cumulative energy input may be greater than 200 kWh/t, greater than400 kWh/t, or greater than 500 kWh/t, or greater than 1,000 kWh/t, orgreater than 1,500 kWh/t, or greater than 2,000 kWh/t, or greater than2,500 kWh/t, or greater than 3,000 kWh/t, or greater than 4,000 kWh/t,or greater than 5,000 kWh/t, or greater than 6,000 kWh/t, or greaterthan 7,000 kWh/t, or between 200 kWh/t and 10,000 kWh/t., or about 200kWh/t and 5,000 kWh/t, or about 200 kWh/t and 4,000 kWh/t, or about 200kWh/t and 3,000 kWh/t, or about 200 kWh/t and 2,000 kWh/t.

In an embodiment of the fourth or fifth aspect of the present invention,the flow cell comprises a cooling jacket for maintaining a temperatureof the suspension of microfibrillated cellulose in the range of about 1°C. to about 80° C., or from about 20° C. to about 50° C., or at roomtemperature, or about 20° C.

In an embodiment of the fourth or fifth aspect of the present invention,the flow cell comprises an adjustable valve at the second outlet tocreate back pressure of the recirculated liquid of from about 0 to about10 bar, or from about 0 to about 4 bar, preferably about 3 bar.

In an embodiment of the fourth or fifth aspect of the present invention,the flow cell further comprises one or more boosters to mechanicallyincrease or decrease the amplitude of the at least one sonication probe.

In an embodiment of the fourth or fifth aspect of the present invention,the liquid composition of microfibrillated cellulose is about 0.5% toabout 10%, or about 0.5% to 5% fibre solids, and in an embodiment of thethird aspect, the liquid composition of microfibrillated cellulose andinorganic particulate material is about 0.5% to about 10%, or about 0.5%to 5% fibre solids.

In an embodiment of the fourth or fifth aspect of the present invention,the ultrasonic energy is applied for about 1 to about 120 minutes, orabout 1 to about 90 minutes, or about 1 to about 75 minutes, or about 1to about 60 minutes, or about 1 to about 45 minutes or about 1 to about30 minutes.

In an embodiment of the fourth aspect of the present invention, themicrofibrillated cellulose may be pelletized, and in the fifth aspect,microfibrillated cellulose and inorganic particulate material may bepelletized.

In an embodiment of the fourth or fifth aspect of the present invention,the recirculation loop may comprise a high shear mixer.

In an embodiment of the fourth or fifth aspect of the present invention,the FLT index for the suspension of microfibrillated cellulose and thesuspension of the microfibrillated cellulose and inorganic particulatematerial may reach 7.5 Nm/g or more, 7.5 Nm/g or more, 8 Nm/g or more,8.5 Nm/g or more, 9 Nm/g or more, 9.5 Nm/g or more, 10 Nm/g or more,10.5 Nm/g or more, 11 Nm/g or more, 11.5 Nm/g or more, 12 Nm/g or more,12.5 Nm/g or more, 13 Nm/g or more, 13.5 Nm/g or more, 14 Nm/g or more,14.5 Nm/g or more, or 15 Nm/g or more, through the methods disclosed inthe specification.

In an embodiment of the fourth or fifth aspect of the present invention,the FLT index may be improved about 5%, about 6%, about 7%, about 7.5%,about 8%, about 9%, about 10%, about 12.5%, about 15% or about 20%, ormore, compared to suspensions of microfibrillated cellulose ormicrofibrillated cellulose and inorganic particulate material producedwithout the application of ultrasonic energy treatment to the slurry orsuspension.

In an embodiment of the fourth or fifth aspect of the present invention,viscosity may be improved by about 5%, about 6%, about 7%, about 7.5%,about 8%, about 9%, about 10%, about 12.5%, about 15% or about 20%, ormore, compared to suspensions of microfibrillated cellulose ormicrofibrillated cellulose and inorganic particulate material producedwithout the application of ultrasonic energy treatment to the slurry orsuspension.

In embodiments of the fourth or fifth aspects of the present invention,the microfibrillated cellulose may be prepared from a chemical pulp, ora chemithermomechanical pulp, or a mechanical pulp, or a recycled pulp,or a paper broke pulp, or a papermill waste stream, or waste from apapermill, or combinations thereof.

In embodiments of the fifth aspect of the present invention, theinorganic particulate material may comprise alkaline earth metalcarbonate or sulphate, such as calcium carbonate, magnesium carbonate,dolomite, gypsum, a hydrous kandite clay such as kaolin, halloysite orball clay, an anhydrous (calcined) kandite clay such as metakaolin orfully calcined kaolin, talc, mica, perlite or diatomaceous earth, orcombinations thereof. In certain embodiments, calcium carbonate and/orkaolin are particularly preferred.

In embodiments of the fourth aspect of the present invention, thesuspensions of microfibrillated cellulose with enhanced viscosity andtensile strength properties obtained by the method are suitable for usein a method of making paper or coating paper, paints and coatings, inks,oilfield chemicals, composites, consumer products, cosmetic products,pharmacological products and food product.

In embodiments of the fifth aspect of the present invention thesuspensions of microfibrillated cellulose and inorganic particulatematerial with enhanced viscosity and tensile strength propertiesobtained by the method are suitable for use in a method of making paperor coating paper, paints and coatings, inks, oilfield chemicals,composites, consumer products, cosmetic products, pharmacologicalproducts and food product.

According to a sixth aspect, the present invention is directed to amethod for preparing an aqueous suspension comprising microfibrillatedcellulose and inorganic particulate material with enhanced viscosity andtensile strength properties, the method comprising a step ofmicrofibrillating a fibrous substrate comprising cellulose and inorganicparticulate material in an aqueous environment in the presence orabsence of a grinding material to produce an aqueous suspensioncomprising microfibrillated cellulose material and inorganic particulatematerial, and further comprising subjecting the aqueous suspensioncomprising microfibrillated cellulose and inorganic particulate materialto sonication to produce the aqueous suspension comprisingmicrofibrillated cellulose and inorganic particulate material withenhanced viscosity and tensile strength properties.

According to a seventh aspect, the present invention is directed to amethod for preparing an aqueous suspension comprising microfibrillatedcellulose with enhanced viscosity and tensile strength properties, themethod comprising a step of microfibrillating a fibrous substratecomprising cellulose in an aqueous environment in the presence of agrinding material to produce an aqueous suspension comprisingmicrofibrillated cellulose material, and further comprising subjectingthe aqueous suspension comprising microfibrillated cellulose tosonication to produce the aqueous suspension comprising microfibrillatedcellulose with enhanced viscosity and tensile strength properties.

According to an eighth aspect, the present invention is directed to amethod for preparing an aqueous suspension comprising microfibrillatedcellulose and inorganic particulate material with enhanced viscosity andtensile strength properties, the method comprising a step ofmicrofibrillating a fibrous substrate comprising cellulose and inorganicparticulate material in an aqueous environment in the presence orabsence of a grinding material to produce an aqueous suspensioncomprising microfibrillated cellulose and inorganic particulatematerial, and further comprising subjecting the aqueous suspensioncomprising microfibrillated cellulose and inorganic particulate materialto a dewatering step (or dehydrating or drying step) to produce apartially dried or dried (e.g., an essentially dried) composition ofmicrofibrillated cellulose and inorganic particulate material, whereuponwhen the partially dried or essentially dried composition ofmicrofibrillated cellulose and inorganic particulate material isreconstituted (or made down) to an aqueous slurry, such aqueous slurryis re-dispersed comprising a sonication step to produce the aqueoussuspension comprising microfibrillated cellulose and inorganicparticulate material with enhanced viscosity and tensile strengthproperties.

According a ninth aspect, the present invention is directed to a methodfor preparing an aqueous suspension comprising microfibrillatedcellulose with enhanced viscosity and tensile strength properties, themethod comprising a step of microfibrillating a fibrous substratecomprising cellulose in an aqueous environment in the presence orabsence of a grinding material to produce an aqueous suspensioncomprising microfibrillated cellulose, and further comprising subjectingthe aqueous suspension comprising microfibrillated cellulose to adewatering step (or dehydrating or drying step) to produce a partiallydried or dried (e.g., an essentially dried) composition ofmicrofibrillated cellulose, whereupon when the partially dried oressentially dried composition of microfibrillated cellulose andinorganic particulate material is reconstituted (or made down) to anaqueous slurry, such aqueous slurry is re-dispersed, comprising asonication step to produce the aqueous suspension comprisingmicrofibrillated cellulose and inorganic particulate material withenhanced viscosity and tensile strength properties.

According to a tenth aspect, the present invention is directed to anaqueous suspension comprising microfibrillated cellulose suitable foruse as filler in paper or a paper coating obtained by a method accordingto the sixth or eighth aspect.

According to a eleventh aspect, the present invention is directed to anaqueous suspension comprising microfibrillated cellulose and inorganicparticulate material suitable for use as filler in paper or a papercoating according to the seventh or ninth aspect.

According to a twelfth aspect, the present invention is directed to apapermaking composition comprising the aqueous suspension of the sixthor eighth aspects.

According to a thirteenth aspect, the present invention is directed to apapermaking composition comprising the aqueous suspension of the seventhor ninth aspects.

According to a fourteenth aspect, the present invention is directed to apaper product prepared from the papermaking composition of the twelfthor thirteenth aspect.

According to a fifteenth aspect, the present invention is directed to apaper coating composition comprising the aqueous suspension comprisingmicrofibrillated cellulose and inorganic particulate material the sixthor eighth aspect and other optional additives.

According to a sixteenth aspect, the present invention is directed to apaper coating composition comprising the aqueous suspension comprisingmicrofibrillated cellulose of the seventh or ninth aspect and otheroptional additives.

According to a seventeenth aspect, the present invention is directed toa paper product, for example paper board, coated with the paper coatingcomposition comprising microfibrillated cellulose and inorganicparticulate material of the sixth or eighth aspect.

According to an eighteenth aspect, the present invention is directed toa paper product, for example paper board, coated with the paper coatingcomposition comprising microfibrillated cellulose of the seventh orninth aspect.

According to a nineteenth aspect, the present invention is directed to aprocess for making a paper product comprising: (i) obtaining orpreparing a fibrous substrate comprising cellulose in the form of a pulpsuitable for making a paper product; (ii) preparing a papermakingcomposition from the pulp in step (i), the aqueous suspension accordingto the first or second aspects of the invention, and other optionaladditives; and (iii) forming a paper product from said papermakingcomposition.

According to a twentieth aspect, the present invention is directed to aprocess for making a paper product comprising: (i) obtaining orpreparing a fibrous substrate comprising cellulose in the form of a pulpsuitable for making a paper product; (ii) preparing a papermakingcomposition from the pulp in step (i), the aqueous suspension accordingto the seventh or ninth aspects of the invention, and other optionaladditives; and (iii) forming a paper product from said papermakingcomposition.

According to a twenty-first aspect, the present invention is directed toan integrated process for making a paper product comprising: (i)obtaining or preparing a fibrous substrate comprising cellulose in theform of a pulp suitable for making a paper product; (ii)microfibrillating a portion of said fibrous substrate comprisingcellulose in accordance with the method of the sixth or eighth aspect ofthe invention to prepare an aqueous suspension comprisingmicrofibrillated and inorganic particulate material; (iii) preparing apapermaking composition from the pulp in step (i), the aqueoussuspension prepared in step (ii), and other optional additives; and (iv)forming a paper product from said papermaking composition.

According to a twenty-second aspect, the present invention is directedto an integrated process for making a paper product comprising: (i)obtaining or preparing a fibrous substrate comprising cellulose in theform of a pulp suitable for making a paper product; (ii)microfibrillating a portion of said fibrous substrate comprisingcellulose in accordance with the method of the seventh or ninth aspectof the invention to prepare an aqueous suspension comprisingmicrofibrillated cellulose; (iii) preparing a papermaking compositionfrom the pulp in step (i), the aqueous suspension prepared in step (ii),and other optional additives; and (iv) forming a paper product from saidpapermaking composition.

According to a twenty-third aspect, the present invention is directed toan integrated process for making a paper product comprising: (i)obtaining or preparing a fibrous substrate comprising cellulose in theform of a pulp suitable for making a paper product; (ii)microfibrillating a portion of said fibrous substrate comprisingcellulose in accordance with the method of the sixth or eighth aspect ofthe invention to prepare an aqueous suspension comprisingmicrofibrillated and inorganic particulate material; (iii) preparing apapermaking composition from the pulp in step (i), the aqueoussuspension prepared in step (ii), and other optional additives; and (iv)forming a paper product from said papermaking composition.

According to a twenty-fourth aspect, the present invention is directedto the use of an aqueous suspension comprising microfibrillatedcellulose according to the sixth or eighth aspect of the invention as afiller in a papermaking composition.

According to a twenty-sixth aspect, the present invention is directed tothe use of an aqueous suspension comprising microfibrillated celluloseand inorganic particulate material according to the sixth or eighthaspect of the invention in a paper coating composition.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a SEM micrograph of microfibrillated cellulose prepared withground calcium carbonate (GCC) in accordance with the methods of thepresent invention.

FIG. 2 shows the effect of exposure to an ultrasonic bath onmicrofibrillated cellulose (MFC) viscosity.

FIG. 3 shows the effect of exposure to an ultrasonic probe on FLT index(Nm/g).

FIG. 4 shows the effect of exposure to an ultrasonic probe onmicrofibrillated cellulose (MFC) viscosity.

FIG. 5 shows the effect of exposure to pulsed ultrasound onmicrofibrillated cellulose (MFC).

FIG. 6 shows the effect of ceramic media contamination onmicrofibrillated cellulose (MFC) exposed to ultrasonication.

FIG. 7 shows the effect of ultrasonication on a 50% percentage of pulp(POP) pressed cake.

FIG. 8 shows the effect of high shear and ultrasonication on amineral-free belt pressed cake.

FIG. 9 shows the effect of ultrasonication on a high solids dry milledbelt pressed cake.

FIG. 10 shows the effect of ultrasonication on a high solids dry milledbelt pressed cake.

FIGS. 11A, B and C show the effect of pressure level at various energyinputs of the sonication probe (sonicator) upon FLT index (a measure oftensile strength), d₅₀ particle size of the microfibrillated celluloseand average power draw in the ultrasonic re-dispersing ofmicrofibrillated cellulose and inorganic particulate material, which hadbeen previously dried and pelletized and then reconstituted,

FIGS. 12A, B, and C show the effect of temperature level at variousenergy inputs of the sonication probe (sonicator) upon FLT index,viscosity and average power draw of the ultrasonic treatment,respectively, in the re-dispersing of microfibrillated cellulose andinorganic particulate material, which had been previously dried andpelletized and then reconstituted

FIGS. 13A and B show the effect of processing with a laboratory highshear mixer to make down previously dried, pelletized and reconstitutedmicrofibrillated cellulose and inorganic particulate materialcomposition at different concentrations upon FLT index and viscosity,respectively, before the application of ultrasonic re-dispersing of themicrofibrillated and inorganic particulate material compositions atvarious energy inputs of the sonication probe (sonicator).

FIGS. 14A, B and C show the effect of continuous process of grinding aliquid slurry of cellulose fibres and inorganic particulate material toproduce microfibrillated cellulose that has never been dewatered ordried, followed by ultrasonic post-treatment processing of the slurry atvarious energy inputs and processing times of the sonication probe(sonicator), upon the FLT index, d₅₀ particle size of themicrofibrillated cellulose and average power draw of the sonicationprobe (sonicator), respectively, on two concentrations ofmicrofibrillated cellulose and inorganic particulate material slurries.

FIGS. 15A, B and C show the effect of using a pulper and a refiner tore-disperse (make down) dried and pelletized microfibrillated celluloseand inorganic particulate material compositions at three different fibresolids contents, prior to treatment with a sonication probe (sonicator),upon FLT index, viscosity and d₅₀ particle size of the microfibrillatedcellulose, respectively.

FIGS. 16A and B show the post-treatment effect of sonication onmicrofibrillated cellulose compositions without inorganic particulatematerial that was produced, respectively by grinding in a stirred mediadetritor and by grinding in a stirred media detritor followed by passagethrough a homogenizer, then followed by ultrasonic treatment at variousenergy inputs, upon the FLT index and d₅₀ particle size of themicrofibrillated cellulose.

DETAILED DESCRIPTION OF THE INVENTION

The Fibrous Substrate Comprising Cellulose

The fibrous substrate comprising cellulose may be derived from anysuitable source, such as wood, grasses (e.g., sugarcane, bamboo) or rags(e.g., textile waste, cotton, hemp or flax). The fibrous substratecomprising cellulose may be in the form of a pulp (i.e., a suspension ofcellulose fibres in water), which may be prepared by any suitablechemical or mechanical treatment, or combination thereof. For example,the pulp may be a chemical pulp, or a chemithermomechanical pulp, or amechanical pulp, or a recycled pulp, or a papermill broke, or apapermill waste stream, or waste from a papermill, or a combinationthereof. The cellulose pulp may be beaten (for example in a Valleybeater) and/or otherwise refined (for example, processing in a conicalor plate refiner) to any predetermined freeness, reported in the art asCanadian standard freeness (CSF) in cm³. CSF means a value for thefreeness or drainage rate of pulp measured by the rate that a suspensionof pulp may be drained. For example, the cellulose pulp may have aCanadian standard freeness of about 10 cm³ or greater prior to beingmicrofibrillated. The cellulose pulp may have a CSF of about 700 cm³ orless, for example, equal to or less than about 650 cm³, or equal to orless than about 600 cm³, or equal to or less than about 550 cm³, orequal to or less than about 500 cm³, or equal to or less than about 450cm³, or equal to or less than about 400 cm³, or equal to or less thanabout 350 cm³, or equal to or less than about 300 cm³, or equal to orless than about 250 cm³, or equal to or less than about 200 cm³, orequal to or less than about 150 cm³, or equal to or less than about 100cm³, or equal to or less than about 50 cm³. The cellulose pulp may thenbe dewatered by methods well known in the art, for example, the pulp maybe filtered through a screen in order to obtain a wet sheet comprisingat least about 10% solids, for example at least about 15% solids, or atleast about 20% solids, or at least about 30% solids, or at least about40% solids. The pulp may be utilized in an unrefined state, that is tosay, without being beaten or dewatered, or otherwise refined.

The fibrous substrate comprising cellulose may be added to a grindingvessel or homogenizer in a dry state. For example, a dry paper broke maybe added directly to the grinder vessel. The aqueous environment in thegrinder vessel will then facilitate the formation of a pulp.

The Inorganic Particulate Material

The inorganic particulate material may, for example, be an alkalineearth metal carbonate or sulphate, such as calcium carbonate, magnesiumcarbonate, dolomite, gypsum, a hydrous kandite clay such as kaolin,halloysite or ball clay, an anhydrous (calcined) kandite clay such asmetakaolin or fully calcined kaolin, talc, mica, perlite or diatomaceousearth, or magnesium hydroxide, or aluminium trihydrate, or combinationsthereof.

A preferred inorganic particulate material for use in the methodaccording to the first aspect of the present invention is calciumcarbonate. Hereafter, the invention may tend to be discussed in terms ofcalcium carbonate, and in relation to aspects where the calciumcarbonate is processed and/or treated. The invention should not beconstrued as being limited to such embodiments.

The particulate calcium carbonate used in the present invention may beobtained from a natural source by grinding. Ground calcium carbonate(GCC) is typically obtained by crushing and then grinding a mineralsource such as chalk, marble or limestone, which may be followed by aparticle size classification step, in order to obtain a product havingthe desired degree of fineness. Other techniques such as bleaching,flotation and magnetic separation may also be used to obtain a producthaving the desired degree of fineness and/or colour. The particulatesolid material may be ground autogeneously, i.e. by attrition betweenthe particles of the solid material themselves, or, alternatively, inthe presence of a particulate grinding medium comprising particles of adifferent material from the calcium carbonate to be ground. Theseprocesses may be carried out with or without the presence of adispersant and biocides, which may be added at any stage of the process.

Precipitated calcium carbonate (PCC) may be used as the source ofparticulate calcium carbonate in the present invention, and may beproduced by any of the known methods available in the art. TAPPIMonograph Series No 30, “Paper Coating Pigments”, pages 34-35 describesthe three main commercial processes for preparing precipitated calciumcarbonate which is suitable for use in preparing products for use in thepaper industry, but may also be used in the practice of the presentinvention. In all three processes, a calcium carbonate feed material,such as limestone, is first calcined to produce quicklime, and thequicklime is then slaked in water to yield calcium hydroxide or milk oflime. In the first process, the milk of lime is directly carbonated withcarbon dioxide gas. This process has the advantage that no by-product isformed, and it is relatively easy to control the properties and purityof the calcium carbonate product. In the second process the milk of limeis contacted with soda ash to produce, by double decomposition, aprecipitate of calcium carbonate and a solution of sodium hydroxide. Thesodium hydroxide may be substantially completely separated from thecalcium carbonate if this process is used commercially. In the thirdmain commercial process the milk of lime is first contacted withammonium chloride to give a calcium chloride solution and ammonia gas.The calcium chloride solution is then contacted with soda ash to produceby double decomposition precipitated calcium carbonate and a solution ofsodium chloride. The crystals can be produced in a variety of differentshapes and sizes, depending on the specific reaction process that isused. The three main forms of PCC crystals are aragonite, rhombohedraland scalenohedral, all of which are suitable for use in the presentinvention, including mixtures thereof.

Wet grinding of calcium carbonate involves the formation of an aqueoussuspension of the calcium carbonate which may then be ground, optionallyin the presence of a suitable dispersing agent. Reference may be madeto, for example, EP-A-614948 (the contents of which are incorporated byreference in their entirety) for more information regarding the wetgrinding of calcium carbonate.

In some circumstances, minor additions of other minerals may beincluded, for example, one or more of kaolin, calcined kaolin,wollastonite, bauxite, talc or mica, could also be present.

When the inorganic particulate material of the present invention isobtained from naturally occurring sources, it may be that some mineralimpurities will contaminate the ground material. For example, naturallyoccurring calcium carbonate can be present in association with otherminerals. Thus, in some embodiments, the inorganic particulate materialincludes an amount of impurities. In general, however, the inorganicparticulate material used in the invention will contain less than about5% by weight, preferably less than about 1% by weight, of other mineralimpurities.

The inorganic particulate material used during the microfibrillatingstep of the method of the present invention will preferably have aparticle size distribution in which at least about 10% by weight of theparticles have an “equivalent spherical diameter” (e.s.d.) of less than2 μm, for example, at least about 20% by weight, or at least about 30%by weight, or at least about 40% by weight, or at least about 50% byweight, or at least about 60% by weight, or at least about 70% byweight, or at least about 80% by weight, or at least about 90% byweight, or at least about 95% by weight, or about 100% of the particleshave an e.s.d. of less than 2 μm.

Unless otherwise stated, particle size properties referred to herein forthe inorganic particulate materials are as measured in a well-knownmanner by sedimentation of the particulate material in a fully dispersedcondition in an aqueous medium using a Sedigraph 5100 machine assupplied by Micromeritics Instruments Corporation, Norcross, Ga., USA(telephone: +1 770 662 3620; web-site: www.micromeritics.com), referredto herein as a “Micromeritics Sedigraph 5100 unit.” Such a machineprovides measurements and a plot of the cumulative percentage by weightof particles having a size, referred to in the art as the “equivalentspherical diameter” (e.s.d.), less than given e.s.d. values. The meanparticle size d₅₀ is the value determined in this way of the particlee.s.d. at which there are 50% by weight of the particles which have anequivalent spherical diameter less than that d₅₀ value.

Alternatively, where stated, the particle size properties referred toherein for the inorganic particulate materials are as measured by thewell-known conventional method employed in the art of laser lightscattering, using a Malvern Mastersizer S machine as supplied by MalvernInstruments Ltd (or by other methods which give essentially the sameresult). In the laser light scattering technique, the size of particlesin powders, suspensions and emulsions may be measured using thediffraction of a laser beam, based on an application of Mie theory. Sucha machine provides measurements and a plot of the cumulative percentageby volume of particles having a size, referred to in the art as the“equivalent spherical diameter” (e.s.d.), less than given e.s.d. values.The mean particle size d₅₀ is the value determined in this way of theparticle e.s.d. at which there are 50% by volume of the particles whichhave an equivalent spherical diameter less than that d₅₀ value.

In another embodiment, the inorganic particulate material used duringthe microfibrillating step of the method of the present invention willpreferably have a particle size distribution, as measured using aMalvern Mastersizer S machine, in which at least about 10% by volume ofthe particles have an e.s.d. of less than 2 μm, for example, at leastabout 20% by volume, or at least about 30% by volume, or at least about40% by volume, or at least about 50% by volume, or at least about 60% byvolume, or at least about 70% by volume, or at least about 80% byvolume, or at least about 90% by volume, or at least about 95% byvolume, or about 100% of the particles by volume have an e.s.d. of lessthan 2 μm.

Unless otherwise stated, particle size properties of themicrofibrillated cellulose materials are as measured by the well-knownconventional method employed in the art of laser light scattering, usinga Malvern Mastersizer S machine as supplied by Malvern Instruments Ltd(or by other methods which give essentially the same result).

Details of the procedure used to characterize the particle sizedistributions of mixtures of inorganic particle material andmicrofibrillated cellulose using a Malvern Mastersizer S machine areprovided below.

Another preferred inorganic particulate material for use in the methodaccording to the first aspect of the present invention is kaolin clay.Hereafter, this section of the specification may tend to be discussed interms of kaolin, and in relation to aspects where the kaolin isprocessed and/or treated. The invention should not be construed as beinglimited to such embodiments. Thus, in some embodiments, kaolin is usedin an unprocessed form.

Kaolin clay used in this invention may be a processed material derivedfrom a natural source, namely raw natural kaolin clay mineral. Theprocessed kaolin clay may typically contain at least about 50% by weightkaolinite. For example, most commercially processed kaolin clays containgreater than about 75% by weight kaolinite and may contain greater thanabout 90%, in some cases greater than about 95% by weight of kaolinite.

Kaolin clay used in the present invention may be prepared from the rawnatural kaolin clay mineral by one or more other processes which arewell known to those skilled in the art, for example by known refining orbeneficiation steps.

For example, the clay mineral may be bleached with a reductive bleachingagent, such as sodium hydrosulfite. If sodium hydrosulfite is used, thebleached clay mineral may optionally be dewatered, and optionally washedand again optionally dewatered, after the sodium hydrosulfite bleachingstep.

The clay mineral may be treated to remove impurities, e.g., byflocculation, flotation, or magnetic separation techniques well known inthe art. Alternatively the clay mineral used in the first aspect of theinvention may be untreated in the form of a solid or as an aqueoussuspension.

The process for preparing the particulate kaolin clay used in thepresent invention may also include one or more comminution steps, e.g.,grinding or milling. Light comminution of a coarse kaolin is used togive suitable delamination thereof. The comminution may be carried outby use of beads or granules of a plastic (e.g., nylon), sand or ceramicgrinding or milling aid. The coarse kaolin may be refined to removeimpurities and improve physical properties using well known procedures.The kaolin clay may be treated by a known particle size classificationprocedure, e.g., screening and centrifuging (or both), to obtainparticles having a desired d₅₀ value or particle size distribution.

The Microfibrillating Process

In accordance with the first aspect of the invention, there is provideda method of preparing a composition for use as a filler in paper or as apaper coating, comprising a step of microfibrillating a fibroussubstrate comprising cellulose in the presence of an inorganicparticulate material. According to particular embodiments of the presentmethods, the microfibrillating step is conducted in the presence of aninorganic particulate material which acts as a microfibrillating agent.By microfibrillating is meant a process in which microfibrils ofcellulose are liberated or partially liberated as individual species oras smaller aggregates as compared to the fibres of thepre-microfibrillated pulp. Typical cellulose fibres (i.e.,pre-microfibrillated pulp) suitable for use in papermaking includelarger aggregates of hundreds or thousands of individual cellulosemicrofibrils. By microfibrillating the cellulose, particularcharacteristics and properties, including but not limited to thecharacteristic and properties described herein, are imparted to themicrofibrillated cellulose and the compositions including themicrofibrillated cellulose.

An exemplary microfibrillated cellulose prepared in accordance with themethods of the present invention is depicted in FIG. 1. FIG. 1 is a SEMmicrograph of microfibrillated cellulose (having a d₅₀ of 80 μm)prepared with GCC (60 wt % <2 μm particle size, by Sedigraph) at 5.0%pulp on total dry weight. The media (Carbolite 16/20) volumeconcentration (MVC) was 50%. The energy input was 2500 kWh/t expressedon fibre.

The step of microfibrillating may be carried out in any suitableapparatus, including but not limited to a refiner. In one embodiment,the microfibrillating step is conducted in a grinding vessel underwet-grinding conditions. In another embodiment, the microfibrillatingstep is carried out in a homogenizer. Each of these embodiments isdescribed in greater detail below.

Wet-Grinding

The grinding is suitably performed in a conventional manner. Thegrinding may be an attrition grinding process in the presence of aparticulate grinding medium, or may be an autogenous grinding process,i.e., one in the absence of a grinding medium. By grinding medium ismeant a medium other than the inorganic particulate material which isco-ground with the fibrous substrate comprising cellulose.

The particulate grinding medium, when present, may be of a natural or asynthetic material. The grinding medium may, for example, compriseballs, beads or pellets of any hard mineral, ceramic or metallicmaterial. Such materials may include, for example, alumina, zirconia,zirconium silicate, aluminium silicate or the mullite-rich materialwhich is produced by calcining kaolinitic clay at a temperature in therange of from about 1300° C. to about 1800° C. For example, in someembodiments a Carbolite® grinding media is preferred. Alternatively,particles of natural sand of a suitable particle size may be used.

Generally, the type of and particle size of grinding medium to beselected for use in the invention may be dependent on the properties,such as, e.g., the particle size of, and the chemical composition of,the feed suspension of material to be ground. Preferably, theparticulate grinding medium comprises particles having an averagediameter in the range of from about 0.1 mm to about 6.0 mm and, morepreferably, in the range of from about 0.2 mm to about 4.0 mm. Thegrinding medium (or media) may be present in an amount up to about 70%by volume of the charge. The grinding media may be present in amount ofat least about 10% by volume of the charge, for example, at least about20% by volume of the charge, or at least about 30% by volume of thecharge, or at least about 40% by volume of the charge, or at least about50% by volume of the charge, or at least about 60% by volume of thecharge.

The grinding may be carried out in one or more stages. For example, acoarse inorganic particulate material may be ground in the grindervessel to a predetermined particle size distribution, after which thefibrous material comprising cellulose is added and the grindingcontinued until the desired level of microfibrillation has beenobtained. The coarse inorganic particulate material used in accordancewith the first aspect of this invention initially may have a particlesize distribution in which less than about 20% by weight of theparticles have an e.s.d. of less than 2 μm, for example, less than about15% by weight, or less than about 10% by weight of the particles have ane.s.d. of less than 2 μm. In another embodiment, the coarse inorganicparticulate material used in accordance with the first aspect of thisinvention initially may have a particle size distribution, as measuredusing a Malvern Mastersizer S machine, in which less than about 20% byvolume of the particles have an e.s.d. of less than 2 μm, for example,less than about 15% by volume, or less than about 1% by volume of theparticles have an e.s.d. of less than 2 μm.

The coarse inorganic particulate material may be wet or dry ground inthe absence or presence of a grinding medium. In the case of a wetgrinding stage, the coarse inorganic particulate material is preferablyground in an aqueous suspension in the presence of a grinding medium. Insuch a suspension, the coarse inorganic particulate material maypreferably be present in an amount of from about 5% to about 85% byweight of the suspension; more preferably in an amount of from about 20%to about 80% by weight of the suspension. Most preferably, the coarseinorganic particulate material may be present in an amount of about 30%to about 75% by weight of the suspension. As described above, the coarseinorganic particulate material may be ground to a particle sizedistribution such that at least about 10% by weight of the particleshave an e.s.d. of less than 2 μm, for example, at least about 20% byweight, or at least about 30% by weight, or at least about 40% byweight, or at least about 50% by weight, or at least about 60% byweight, or at least about 70% by weight, or at least about 80% byweight, or at least about 90% by weight, or at least about 95% byweight, or about 100% by weight of the particles, have an e.s.d. of lessthan 2 μm, after which the cellulose pulp is added and the twocomponents are co-ground to microfibrillate the fibres of the cellulosepulp.

In another embodiment, the coarse inorganic particulate material isground to a particle size distribution, as measured using a MalvernMastersizer S machine such that at least about 10% by volume of theparticles have an e.s.d. of less than 2 μm, for example, at least about20% by volume, or at least about 30% by volume or at least about 40% byvolume, or at least about 50% by volume, or at least about 60% byvolume, or at least about 70% by volume, or at least about 80% byvolume, or at least about 90% by volume, or at least about 95% byvolume, or about 100% by volume of the particles, have an e.s.d. of lessthan 2 μm, after which the cellulose pulp is added and the twocomponents are co-ground to microfibrillate the fibres of the cellulosepulp.

In one embodiment, the mean particle size (d₅₀) of the inorganicparticulate material is reduced during the co-grinding process. Forexample, the d₅₀ of the inorganic particulate material may be reduced byat least about 10% (as measured by a Malvern Mastersizer S machine), forexample, the d₅₀ of the inorganic particulate material may be reduced byat least about 20%, or reduced by at least about 30%, or reduced by atleast about 50%, or reduced by at least about 50%, or reduced by atleast about 60%, or reduced by at least about 70%, or reduced by atleast about 80%, or reduced by at least about 90%. For example, aninorganic particulate material having a d₅₀ of 2.5 μm prior toco-grinding and a d₅₀ of 1.5 μm post co-grinding will have been subjectto a 40% reduction in particle size. In embodiments, the mean particlesize of the inorganic particulate material is not significantly reducedduring the co-grinding process. By “not significantly reduced” is meantthat the d₅₀ of the inorganic particulate material is reduced by lessthan about 10%, for example, the d₅₀ of the inorganic particulatematerial is reduced by less than about 5%.

The fibrous substrate comprising cellulose may be microfibrillated inthe presence of an inorganic particulate material to obtainmicrofibrillated cellulose having a d₅₀ ranging from about 5 to μm about500 μm, as measured by laser light scattering. The fibrous substratecomprising cellulose may be microfibrillated in the presence of aninorganic particulate material to obtain microfibrillated cellulosehaving a d₅₀ of equal to or less than about 400 μm, for example equal toor less than about 300 μm, or equal to or less than about 200 μm, orequal to or less than about 150 μm, or equal to or less than about 125μm, or equal to or less than about 100 μm, or equal to or less thanabout 90 μm, or equal to or less than about 80 μm, or equal to or lessthan about 70 μm, or equal to or less than about 60 μm, or equal to orless than about 50 μm, or equal to or less than about 40 μm, or equal toor less than about 30 μm, or equal to or less than about 20 μm, or equalto or less than about 10 μm.

The fibrous substrate comprising cellulose may be microfibrillated inthe presence of an inorganic particulate material to obtainmicrofibrillated cellulose having a modal fibre particle size rangingfrom about 0.1-500 μm and a modal inorganic particulate materialparticle size ranging from 0.25-20 μm. The fibrous substrate comprisingcellulose may be microfibrillated in the presence of an inorganicparticulate material to obtain microfibrillated cellulose having a modalfibre particle size of at least about 0.5 μm, for example at least about10 μm, or at least about 50 μm, or at least about 100 μm, or at leastabout 150 μm, or at least about 200 μm, or at least about 300 μm, or atleast about 400 μm.

The fibrous substrate comprising cellulose may be microfibrillated inthe presence of an inorganic particulate material to obtainmicrofibrillated cellulose having a fibre steepness equal to or greaterthan about 10, as measured by Malvern. Fibre steepness (i.e., thesteepness of the particle size distribution of the fibres) is determinedby the following formula:Steepness=100×(d ₃₀ /d ₇₀)

The microfibrillated cellulose may have a fibre steepness equal to orless than about 100. The microfibrillated cellulose may have a fibresteepness equal to or less than about 75, or equal to or less than about50, or equal to or less than about 40, or equal to or less than about30. The microfibrillated cellulose may have a fibre steepness from about20 to about 50, or from about 25 to about 40, or from about 25 to about35, or from about 30 to about 40.

The grinding is suitably performed in a grinding vessel, such as atumbling mill (e.g., rod, ball and autogenous), a stirred mill (e.g.,SAM or IsaMill), a tower mill, a stirred media detritor (SMD), or agrinding vessel comprising rotating parallel grinding plates betweenwhich the feed to be ground is fed.

In one embodiment, the grinding vessel is a tower mill. The tower millmay comprise a quiescent zone above one or more grinding zones. Aquiescent zone is a region located towards the top of the interior oftower mill in which minimal or no grinding takes place and comprisesmicrofibrillated cellulose and inorganic particulate material. Thequiescent zone is a region in which particles of the grinding mediumsediment down into the one or more grinding zones of the tower mill.

The tower mill may comprise a classifier above one or more grindingzones. In an embodiment, the classifier is top mounted and locatedadjacent to a quiescent zone. The classifier may be a hydrocyclone.

The tower mill may comprise a screen above one or more grind zones. Inan embodiment, a screen is located adjacent to a quiescent zone and/or aclassifier. The screen may be sized to separate grinding media from theproduct aqueous suspension comprising microfibrillated cellulose andinorganic particulate material and to enhance grinding mediasedimentation.

In an embodiment, the grinding is performed under plug flow conditions.Under plug flow conditions the flow through the tower is such that thereis limited mixing of the grinding materials through the tower. Thismeans that at different points along the length of the tower mill theviscosity of the aqueous environment will vary as the fineness of themicrofibrillated cellulose increases. Thus, in effect, the grindingregion in the tower mill can be considered to comprise one or moregrinding zones which have a characteristic viscosity. A skilled personin the art will understand that there is no sharp boundary betweenadjacent grinding zones with respect to viscosity.

In an embodiment, water is added at the top of the mill proximate to thequiescent zone or the classifier or the screen above one or moregrinding zones to reduce the viscosity of the aqueous suspensioncomprising microfibrillated cellulose and inorganic particulate materialat those zones in the mill. By diluting the product microfibrillatedcellulose and inorganic particulate material at this point in the millit has been found that the prevention of grinding media carry over tothe quiescent zone and/or the classifier and/or the screen is improved.Further, the limited mixing through the tower allows for processing athigher solids lower down the tower and dilute at the top with limitedbackflow of the dilution water back down the tower into the one or moregrinding zones. Any suitable amount of water which is effective todilute the viscosity of the product aqueous suspension comprisingmicrofibrillated cellulose and inorganic particulate material may beadded. The water may be added continuously during the grinding process,or at regular intervals, or at irregular intervals.

In another embodiment, water may be added to one or more grinding zonesvia one or more water injection points positioned along the length ofthe tower mill, or each water injection point being located at aposition which corresponds to the one or more grinding zones.Advantageously, the ability to add water at various points along thetower allows for further adjustment of the grinding conditions at any orall positions along the mill.

The tower mill may comprise a vertical impeller shaft equipped with aseries of impeller rotor disks throughout its length. The action of theimpeller rotor disks creates a series of discrete grinding zonesthroughout the mill.

In another embodiment, the grinding is performed in a screened grinder,preferably a stirred media detritor. The screened grinder may compriseone or more screen(s) having a nominal aperture size of at least about250 μm, for example, the one or more screens may have a nominal aperturesize of at least about 300 μm, or at least about 350 μm, or at leastabout 400 μm, or at least about 450 μm, or at least about 500 μm, or atleast about 550 μm, or at least about 600 μm, or at least about 650 μm,or at least about 700 μm, or at least about 750 μm, or at least about800 μm, or at least about 850 μm, or at or least about 900 μm, or atleast about 1000 μm.

The screen sizes noted immediately above are applicable to the towermill embodiments described above.

As noted above, the grinding may be performed in the presence of agrinding medium. In an embodiment, the grinding medium is a coarse mediacomprising particles having an average diameter in the range of fromabout 1 mm to about 6 mm, for example about 2 mm, or about 3 mm, orabout 4 mm, or about 5 mm.

In another embodiment, the grinding media has a specific gravity of atleast about 2.5, for example, at least about 3, or at least about 3.5,or at least about 4.0, or at least about 4.5, or least about 5.0, or atleast about 5.5, or at least about 6.0.

In another embodiment, the grinding media comprises particles having anaverage diameter in the range of from about 1 mm to about 6 mm and has aspecific gravity of at least about 2.5.

In another embodiment, the grinding media comprises particles having anaverage diameter of about 3 mm and specific gravity of about 2.7.

As described above, the grinding medium (or media) may present in anamount up to about 70% by volume of the charge. The grinding media maybe present in amount of at least about 10% by volume of the charge, forexample, at least about 20% by volume of the charge, or at least about30% by volume of the charge, or at least about 40% by volume of thecharge, or at least about 50% by volume of the charge, or at least about60% by volume of the charge. In one embodiment, the grinding medium ispresent in amount of about 50% by volume of the charge.

By “charge’ is meant the composition which is the feed fed to thegrinder vessel. The charge includes water, grinding media, and fibroussubstrate comprising cellulose and inorganic particulate material, andany other optional additives as described herein.

The use of a relatively coarse and/or dense media has the advantage ofimproved (i.e., faster) sediment rates and reduced media carry overthrough the quiescent zone and/or classifier and/or screen(s).

A further advantage in using relatively coarse grinding media is thatthe mean particle size (d₅₀) of the inorganic particulate material maynot be significantly reduced during the grinding process such that theenergy imparted to the grinding system is primarily expended inmicrofibrillating the fibrous substrate comprising cellulose.

A further advantage in using relatively coarse screens is that arelatively coarse or dense grinding media can be used in themicrofibrillating step. In addition, the use of relatively coarsescreens (i.e., having a nominal aperture of least about 250 μm) allows arelatively high solids product to be processed and removed from thegrinder, which allows a relatively high solids feed (comprising fibroussubstrate comprising cellulose and inorganic particulate material) to beprocessed in an economically viable process. As discussed below, it hasbeen found that a feed having a high initial solids content is desirablein terms of energy sufficiency. Further, it has also been found thatproduct produced (at a given energy) at lower solids has a coarserparticle size distribution.

As discussed in the ‘Background’ section above, the present inventionseeks to address the problem of preparing microfibrillated celluloseeconomically on an industrial scale.

Thus, in accordance with one embodiment, the fibrous substratecomprising cellulose and inorganic particulate material are present inthe aqueous environment at an initial solids content of at least about 4wt. %, of which at least about 2% by weight is fibrous substratecomprising cellulose. The initial solids content may be at least about10 wt. %, or at least about 20 wt. %, or at least about 30 wt. %, or atleast about at least 40 wt. %. At least about 5% by weight of theinitial solids content may be fibrous substrate comprising cellulose,for example, at least about 10%, or at least about 15%, or at leastabout 20% by weight of the initial solids content may be fibroussubstrate comprising cellulose.

In another embodiment, the grinding is performed in a cascade ofgrinding vessels, one or more of which may comprise one or more grindingzones. For example, the fibrous substrate comprising cellulose and theinorganic particulate material may be ground in a cascade of two or moregrinding vessels, for example, a cascade of three or more grindingvessels, or a cascade of four or more grinding vessels, or a cascade offive or more grinding vessels, or a cascade of six or more grindingvessels, or a cascade of seven or more grinding vessels, or a cascade ofeight or more grinding vessels, or a cascade of nine or more grindingvessels in series, or a cascade comprising up to ten grinding vessels.The cascade of grinding vessels may be operatively linked in series orparallel or a combination of series and parallel. The output from and/orthe input to one or more of the grinding vessels in the cascade may besubjected to one or more screening steps and/or one or moreclassification steps.

The total energy expended in a microfibrillation process may beapportioned equally across each of the grinding vessels in the cascade.Alternatively, the energy input may vary between some or all of thegrinding vessels in the cascade.

A person skilled in the art will understand that the energy expended pervessel may vary between vessels in the cascade depending on the amountof fibrous substrate being microfibrillated in each vessel, andoptionally the speed of grind in each vessel, the duration of grind ineach vessel, the type of grinding media in each vessel and the type andamount of inorganic particulate material. The grinding conditions may bevaried in each vessel in the cascade in order to control the particlesize distribution of both the microfibrillated cellulose and theinorganic particulate material. For example, the grinding media size maybe varied between successive vessels in the cascade in order to reducegrinding of the inorganic particulate material and to target grinding ofthe fibrous substrate comprising cellulose.

In an embodiment the grinding is performed in a closed circuit. Inanother embodiment, the grinding is performed in an open circuit. Thegrinding may be performed in batch mode. The grinding may be performedin a re-circulating batch mode.

As described above, the grinding circuit may include a pre-grinding stepin which coarse inorganic particulate ground in a grinder vessel to apredetermined particle size distribution, after which fibrous materialcomprising cellulose is combined with the pre-ground inorganicparticulate material and the grinding continued in the same or differentgrinding vessel until the desired level of microfibrillation has beenobtained.

As the suspension of material to be ground may be of a relatively highviscosity, a suitable dispersing agent may preferably be added to thesuspension prior to grinding. The dispersing agent may be, for example,a water soluble condensed phosphate, polysilicic acid or a salt thereof,or a polyelectrolyte, for example a water soluble salt of a poly(acrylicacid) or of a poly(methacrylic acid) having a number average molecularweight not greater than 80,000. The amount of the dispersing agent usedwould generally be in the range of from 0.1 to 2.0% by weight, based onthe weight of the dry inorganic particulate solid material. Thesuspension may suitably be ground at a temperature in the range of from4° C. to 100° C.

Other additives which may be included during the microfibrillation stepinclude: carboxymethyl cellulose, amphoteric carboxymethyl cellulose,oxidising agents, 2,2,6,6-Tetramethylpiperidine-1-oxyl (TEMPO), TEMPOderivatives, and wood degrading enzymes.

The pH of the suspension of material to be ground may be about 7 orgreater than about 7 (i.e., basic), for example, the pH of thesuspension may be about 8, or about 9, or about 10, or about 11. The pHof the suspension of material to be ground may be less than about 7(i.e., acidic), for example, the pH of the suspension may be about 6, orabout 5, or about 4, or about 3. The pH of the suspension of material tobe ground may be adjusted by addition of an appropriate amount of acidor base. Suitable bases included alkali metal hydroxides, such as, forexample NaOH. Other suitable bases are sodium carbonate and ammonia.Suitable acids included inorganic acids, such as hydrochloric andsulphuric acid, or organic acids. An exemplary acid is orthophosphoricacid.

The amount of inorganic particulate material and cellulose pulp in themixture to be co-ground may vary in a ratio of from about 99.5:0.5 toabout 0.5:99.5, based on the dry weight of inorganic particulatematerial and the amount of dry fibre in the pulp, for example, a ratioof from about 99.5:0.5 to about 50:50 based on the dry weight ofinorganic particulate material and the amount of dry fibre in the pulp.For example, the ratio of the amount of inorganic particulate materialand dry fibre may be from about 99.5:0.5 to about 70:30. In anembodiment, the ratio of inorganic particulate material to dry fibre isabout 80:20, or for example, about 85:15, or about 90:10, or about 91:9,or about 92:8, or about 93:7, or about 94:6, or about 95:5, or about96:4, or about 97:3, or about 98:2, or about 99:1. In a preferredembodiment, the weight ratio of inorganic particulate material to dryfibre is about 95:5. In another preferred embodiment, the weight ratioof inorganic particulate material to dry fibre is about 90:10. Inanother preferred embodiment, the weight ratio of inorganic particulatematerial to dry fibre is about 85:15. In another preferred embodiment,the weight ratio of inorganic particulate material to dry fibre is about80:20. In another preferred embodiment, the weight ratio of inorganicparticulate material to dry fibre is about 50:50.

The total energy input in a typical grinding process to obtain thedesired aqueous suspension composition may typically be between about100 and 1500 kWht⁻¹ based on the total dry weight of the inorganicparticulate filler. The total energy input may be less than about 1000kWht⁻¹, for example, less than about 800 kWht⁻¹, less than about 600kWht⁻¹, less than about 500 kWht⁻¹, less than about 400 kWht⁻¹, lessthan about 300 kWht⁻¹, or less than about 200 kWht⁻¹. As such, thepresent inventors have surprisingly found that a cellulose pulp can bemicrofibrillated at relatively low energy input when it is co-ground inthe presence of an inorganic particulate material. As will be apparent,the total energy input per tonne of dry fibre in the fibrous substratecomprising cellulose will be less than about 10,000 kWht⁻¹, for example,less than about 9000 kWht⁻¹, or less than about 8000 kWht⁻¹, or lessthan about 7000 kWht⁻¹, or less than about 6000 kWht⁻¹, or less thanabout 5000 kWht⁻¹, for example less than about 4000 kWht⁻¹, less thanabout 3000 kWht⁻¹, less than about 2000 kWht⁻¹, less than about 1500kWht⁻¹. less than about 1200 kWht⁻¹, less than about 1000 kWht⁻¹, orless than about 800 kWht⁻¹. The total energy input varies depending onthe amount of dry fibre in the fibrous substrate being microfibrillated,and optionally the speed of grind and the duration of grind.

Homogenizing

Microfibrillation of the fibrous substrate comprising cellulose may beeffected under wet conditions in the presence of the inorganicparticulate material by a method in which the mixture of cellulose pulpand inorganic particulate material is pressurized (for example, to apressure of about 500 bar) and then passed to a zone of lower pressure.The rate at which the mixture is passed to the low pressure zone issufficiently high and the pressure of the low pressure zone issufficiently low as to cause microfibrillation of the cellulose fibres.For example, the pressure drop may be effected by forcing the mixturethrough an annular opening that has a narrow entrance orifice with amuch larger exit orifice. The drastic decrease in pressure as themixture accelerates into a larger volume (i.e., a lower pressure zone)induces cavitation which causes microfibrillation. In an embodiment,microfibrillation of the fibrous substrate comprising cellulose may beeffected in a homogenizer under wet conditions in the presence of theinorganic particulate material. In the homogenizer, the cellulosepulp-inorganic particulate material mixture is pressurized (for example,to a pressure of about 500 bar), and forced through a small nozzle ororifice. The mixture may be pressurized to a pressure of from about 100to about 1000 bar, for example to a pressure of equal to or greater than300 bar, or equal to or greater than about 500, or equal to or greaterthan about 200 bar, or equal to or greater than about 700 bar. Thehomogenization subjects the fibres to high shear forces such that as thepressurized cellulose pulp exits the nozzle or orifice, cavitationcauses microfibrillation of the cellulose fibres in the pulp. Additionalwater may be added to improve flowability of the suspension through thehomogenizer. The resulting aqueous suspension comprisingmicrofibrillated cellulose and inorganic particulate material may be fedback into the inlet of the homogenizer for multiple passes through thehomogenizer. In a preferred embodiment, the inorganic particulatematerial is a naturally platy mineral, such as kaolin. As such,homogenization not only facilitates microfibrillation of the cellulosepulp, but also facilitates delamination of the platy particulatematerial.

A platy particulate material, such as kaolin, is understood to have ashape factor of at least about 10, for example, at least about 15, or atleast about 20, or at least about 30, or at least about 40, or at leastabout 50, or at least about 60, or at least about 70, or at least about80, or at least about 90, or at least about 100. Shape factor, as usedherein, is a measure of the ratio of particle diameter to particlethickness for a population of particles of varying size and shape asmeasured using the electrical conductivity methods, apparatuses, andequations described in U.S. Pat. No. 5,576,617, which is incorporatedherein by reference.

A suspension of a platy inorganic particulate material, such as kaolin,may be treated in the homogenizer to a predetermined particle sizedistribution in the absence of the fibrous substrate comprisingcellulose, after which the fibrous material comprising cellulose isadded to the aqueous slurry of inorganic particulate material and thecombined suspension is processed in the homogenizer as described above.The homogenization process is continued, including one or more passesthrough the homogenizer, until the desired level of microfibrillationhas been obtained. Similarly, the platy inorganic particulate materialmay be treated in a grinder to a predetermined particle sizedistribution and then combined with the fibrous material comprisingcellulose followed by processing in the homogenizer.

An exemplary homogenizer is a Manton Gaulin (APV) homogenizer.

After the microfibrillation step has been carried out, the aqueoussuspension comprising microfibrillated cellulose and inorganicparticulate material may be screened to remove fibre above a certainsize and to remove any grinding medium. For example, the suspension canbe subjected to screening using a sieve having a selected nominalaperture size in order to remove fibres which do not pass through thesieve. Nominal aperture size means the nominal central separation ofopposite sides of a square aperture or the nominal diameter of a roundaperture. The sieve may be a BSS sieve (in accordance with BS 1796)having a nominal aperture size of 150 μm, for example, a nominalaperture size 125 μm, or 106 μm, or 90 μm, or 74 μm, or 63 μm, or 53 μm,45 μm, or 38 μm. In one embodiment, the aqueous suspension is screenedusing a BSS sieve having a nominal aperture of 125 μm. The aqueoussuspension may then be optionally dewatered.

The Aqueous Suspension

The aqueous suspensions of this invention produced in accordance withthe methods described above are suitable for use in a method of makingpaper or coating paper.

As such, the present invention is directed to an aqueous suspensioncomprising, consisting of, or consisting essentially of microfibrillatedcellulose and an inorganic particulate material and other optionaladditives. The aqueous suspension is suitable for use in a method ofmaking paper or coating paper. The other optional additives includedispersant, biocide, suspending aids, salt(s) and other additives, forexample, starch or carboxymethylcellulose or polymers, which mayfacilitate the interaction of mineral particles and fibres during orafter grinding.

The inorganic particulate material may have a particle size distributionsuch that at least about 10% by weight, for example at least about 20%by weight, for example at least about 30% by weight, for example atleast about 40% by weight, for example at least about 50% by weight, forexample at least about 60% by weight, for example at least about 70% byweight, for example at least about 80% by weight, for example at leastabout 90% by weight, for example at least about 95% by weight, or forexample about 100% of the particles have an e.s.d. of less than 2 μm.

In another embodiment, the inorganic particulate material may have aparticle size distribution, as measured by a Malvern Mastersizer Smachine, such that at least about 10% by volume, for example at leastabout 20% by volume, for example at least about 30% by volume, forexample at least about 40% by volume, for example at least about 50% byvolume, for example at least about 60% by volume, for example at leastabout 70% by volume, for example at least about 80% by volume, forexample at least about 90% by volume, for example at least about 95% byvolume, or for example about 100% by volume of the particles have ane.s.d. of less than 2 μm.

The amount of inorganic particulate material and cellulose pulp in themixture to be co-ground may vary in a ratio of from about 99.5:0.5 toabout 0.5:99.5, based on the dry weight of inorganic particulatematerial and the amount of dry fibre in the pulp, for example, a ratioof from about 99.5:0.5 to about 50:50 based on the dry weight ofinorganic particulate material and the amount of dry fibre in the pulp.For example, the ratio of the amount of inorganic particulate materialand dry fibre may be from about 99.5:0.5 to about 70:30. In anembodiment, the ratio of inorganic particulate material to dry fibre isabout 80:20, or for example, about 85:15, or about 90:10, or about 91:9,or about 92:8, or about 93:7, or about 94:6, or about 95:5, or about96:4, or about 97:3, or about 98:2, or about 99:1. In a preferredembodiment, the weight ratio of inorganic particulate material to dryfibre is about 95:5. In another preferred embodiment, the weight ratioof inorganic particulate material to dry fibre is about 90:10. Inanother preferred embodiment, the weight ratio of inorganic particulatematerial to dry fibre is about 85:15. In another preferred embodiment,the weight ratio of inorganic particulate material to dry fibre is about80:20. In another preferred embodiment, the weight ratio of inorganicparticulate material to dry fibre is about 50:50.

In an embodiment, the composition does not include fibres too large topass through a BSS sieve (in accordance with BS 1796) having a nominalaperture size of 150 μm, for example, a nominal aperture size of 125 μm,106 μm, or 90 μm, or 74 μm, or 63 μm, or 53 μm, 45 μm, or 38 μm. In oneembodiment, the aqueous suspension is screened using a BSS sieve havinga nominal aperture of 125 μm.

It will be understood therefore that amount (i.e., % by weight) ofmicrofibrillated cellulose in the aqueous suspension after grinding orhomogenizing may be less than the amount of dry fibre in the pulp if theground or homogenized suspension is treated to remove fibres above aselected size. Thus, the relative amounts of pulp and inorganicparticulate material fed to the grinder or homogenizer can be adjusteddepending on the amount of microfibrillated cellulose that is requiredin the aqueous suspension after fibres above a selected size areremoved.

In an embodiment, the inorganic particulate material is an alkalineearth metal carbonate, for example, calcium carbonate. The inorganicparticulate material may be ground calcium carbonate (GCC) orprecipitated calcium carbonate (PCC), or a mixture of GCC and PCC. Inanother embodiment, the inorganic particulate material is a naturallyplaty mineral, for example, kaolin. The inorganic particulate materialmay be a mixture of kaolin and calcium carbonate, for example, a mixtureof kaolin and GCC, or a mixture of kaolin and PCC, or a mixture ofkaolin, GCC and PCC.

In another embodiment, the aqueous suspension is treated to remove atleast a portion or substantially all of the water to form a partiallydried or essentially completely dried product. For example, at leastabout 10% by volume of water in the aqueous suspension may be removedfrom the aqueous suspension, for example, at least about 20% by volume,or at least about 30% by volume, or least about 40% by volume, or atleast about 50% by volume, or at least about 60% by volume, or at leastabout 70% by volume or at least about 80% by volume or at least about90% by volume, or at least about 100% by volume of water in the aqueoussuspension may be removed. Any suitable technique can be used to removewater from the aqueous suspension including, for example, by gravity orvacuum-assisted drainage, with or without pressing, or by evaporation,or by filtration, or by a combination of these techniques. The partiallydried or essentially completely dried product will comprisemicrofibrillated cellulose and inorganic particulate material and anyother optional additives that may have been added to the aqueoussuspension prior to drying. The partially dried or essentiallycompletely dried product may be stored or packaged for sale. Thepartially dried or essentially completely dried product may beoptionally re-hydrated and incorporated in papermaking compositions andother paper products, as described herein.

The Ultrasonication Process

In brief, sonication, ultrasonication or ultrasonification (herein usedinterchangeably unless otherwise noted) is the irradiation of a liquidsample with ultrasonic (>20 kHz. e.g., 20 to 100 kHz) sound waves whichresults in agitation of the liquid. The sound waves propagate into aliquid media resulting in alternating high-pressure (compression) andlow-pressure (rarefaction) cycles. During rarefaction, high-intensitysonic waves create small vacuum bubbles or voids in the liquid, whichthen collapse violently (cavitation) during compression, creating veryhigh local temperatures, and agitation. The combination of these eventsresults in high shear forces capable of breaking down or reducingmaterials into smaller constituents essentially emulsifying thematerial. This process may change physical properties of the materialdepending on the operation parameters chosen.

Ultrasonication can be used to re-disperse and de-agglomerate dewatered,partially dried or essentially dried microfibrillated cellulosecontaining compositions. The main applications of ultrasonics includehomogenization (mixing), dispersing, de-agglomeration, wet-milling andgrinding (e.g. nano-materials), emulsifying, and cell disintegration.Ultrasonication also aids in mixing of materials through the agitationof the material. Although the present invention is not limited to theuse of any particular sonication device, ultrasonication is mosttypically performed by use of an ultrasonic bath or an ultrasonic probe(or transducer). Suitable devices known in the art also include, and arenot limited to an ultrasonic homogenizer, an ultrasonic foil and anultrasonic horn. Commercial scale ultrasonication devices are availablefrom Hielscher Ultrasonics GmbH (Oderstr. 53 D-14513 Teltow, Germany and530 Ringwood Ave. Lembo & Gray Bldg. Wanaque, N.J. 07465, USA). Suitablesonification probes are variously called sonotrodes and cascotrodes bythe foregoing manufacturer

In trials reported in some of the Examples in this specification, apilot scale ultrasonic probe (sonotrode) from Hielscher was utilized. Insuch trials, the unit was utilized with a 3 L/min progressive cavity(seepex) pump.

In trials reported in certain Examples below, the trials were conductedin recirculation mode between the feed tank and the ultrasonic flow cell(this is where the sonication probe (sonotrode, i.e. the device thatdirects ultrasonic energy to the slurry, is located)).

The starting volume in the feed tank for the reported trials was 2.5 L.250 ml samples were collected after 0, 1, 2, 4 and 10 min of sonication.The flow rate during all such trials was maintained at approximately 1.5L/min. In addition, several processing configurations were possibleusing various combinations of boosters (B4-1.8 and B4-2.2) andsonotrodes (BS4d22 and BS4d40) to determine the configuration in theprocessing of various microfibrillated cellulose or microfibrillatedcellulose and inorganic particulate material feed products. Sonotrodesare used to directly transfer the ultrasonic energy generated by atransducer to the medium/slurry to be sonified. Boosters are used tomechanically increase (or decrease) the amplitude generated bysonotrodes.

Any effects of ultrasonication-induced cavitation on a material arecontrolled through a combination of parameters including differentfrequencies, displacement or vibration amplitudes, time of exposure tothe process and mode of administration of the process (e.g., pulsed orcontinuous administration). Frequencies used typically range from about20 to about 100 kHz, or from about 25 to about 55 kHz. Amplitudes usedtypically range from about 22 to about 50 μm. Operating pressures offrom 0 to 10 bar, or 0 to 4 bar, preferably about 3 bar may be utilized.Temperatures of 20° C. to 50° C. are suitable. Optimal conditions forsonification of slurries of microfibrillated cellulose ormicrofibrillated cellulose and inorganic particulate material were foundto be 3 bar pressure, 20° C. and 1.5 wt. % fibre solids. The choice ofusing an ultrasonic bath, ultrasonic probe or other device can alsoinfluence the end result of the process.

With regard to the present invention, it has been found thatultrasonication of the aqueous suspension comprising themicrofibrillated cellulose or microfibrillated cellulose and aninorganic particulate material of the present invention (collectivelyreferred to as the “aqueous suspension”) enhances physical properties ofthe material. For example, ultrasonication of an aqueous suspensioncomprising microfibrillated cellulose or comprising microfibrillatedcellulose and an inorganic particulate material surprisingly andunexpectedly results in enhanced viscosity and/or tensile strength ofthe material, as demonstrated in the Examples section of thisspecification. The enhancement of the physical properties of thematerial of the present invention and the degree of enhancement isdependent upon the operating parameters used. In view of the teachingsof this specification, one of ordinary skill in the art will be able todiscern the parameters appropriate to achieve a desired result withoutundue experimentation.

In an aspect of the present invention, the ultrasonication of theaqueous suspension of the present invention comprises producing asonicated suspension comprising microfibrillated cellulose and inorganicparticulate material with enhanced viscosity and/or tensile strengthproperties, the method comprising a step of microfibrillating a fibroussubstrate comprising cellulose in an aqueous environment in the presenceof an inorganic particulate material to produce an aqueous suspensioncomprising microfibrillated cellulose and inorganic particulatematerial, and further comprising subjecting the aqueous suspensioncomprising microfibrillated cellulose and inorganic particulate materialto sonication to produce the aqueous suspension comprisingmicrofibrillated cellulose and inorganic particulate material withenhanced viscosity and tensile strength properties. Themicrofibrillating step may comprise grinding the fibrous substratecomprising cellulose in the presence of the inorganic particulatematerial and may further comprise an initial step of grinding theinorganic particulate material in the absence of the fibrous substratecomprising cellulose to obtain an inorganic particulate material havinga desired particle size.

In one embodiment, a grinding media, as discussed above, may also beused to produce the aqueous suspension comprising microfibrillatedcellulose and inorganic particulate material with enhanced viscosity andtensile strength properties.

Ultrasonication of the aqueous suspension comprising microfibrillatedcellulose and inorganic particulate material may be conducted with anultrasonic probe or ultrasonic water bath, an ultrasonic homogenizer, anultrasonic foil or an ultrasonic horn. The use of such devices is knownto one of ordinary skill in the art.

In an embodiment of the present invention, the methods of the presentinvention may further comprise one or more of high shear mixing,homogenisation or refining either before or after the sonication step,all of which are known by one of ordinary skill in the art and may beincorporated into the methods of the present invention without undueexperimentation in view of the teachings of this specification.

Re-Dispersion of Dewatered, Partially Dried or Essentially DriedMicrofibrillated Cellulose Compositions, Optionally Containing InorganicParticulate Material.

In an embodiment, ultrasonication is advantageously used to re-dispersepreviously dewatered, partially dried or essentially dried compositionsof microfibrillated cellulose or compositions of microfibrillatedcellulose and inorganic particulate material. The dewatered partiallydried or essentially dried compositions of microfibrillated cellulose orcompositions of microfibrillated cellulose and inorganic particulatematerial may be pelletized after dewatering and drying. Such dewatered,partially dried or essentially dried, and optionally pelletized,compositions of microfibrillated cellulose or compositions ofmicrofibrillated cellulose and inorganic particulate material arere-suspended with the aid of ultrasonication devices of the typesdescribed in this specification.

In an embodiment ultrasonication is used as a post-treatment step forslurries of microfibrillated cellulose or compositions ofmicrofibrillated cellulose and inorganic particulate material to improveone or more physical property of such slurries, for example, increasedtensile strength and enhanced viscosity.

In an embodiment, the inventors have invented a method for re-dispersingdewatered, partially dried or essentially dried microfibrillatedcellulose, the method comprising the steps of:

-   -   (a) adding a quantity of a suitable dispersing liquid to a tank        having at least one inlet and an outlet, wherein the tank        further comprises a mixer and a pump attached to the outlet;    -   (b) adding a quantity of dewatered, partially dried or        essentially dried microfibrillated cellulose to the tank through        the at least one inlet in sufficient quantity to yield a liquid        composition of microfibrillated cellulose at a desired solids        concentration;    -   (c) mixing the dispersing liquid and the dewatered, partially        dried or essentially dried microfibrillated cellulose in the        tank with the mixer to partially de-agglomerate and re-disperse        the microfibrillated cellulose to form a flowable slurry;    -   (d) pumping the flowable slurry with the pump to an inlet of a        flow cell, wherein the flow cell comprises one or more        sonication probe in series and at least one outlet;    -   (e) applying ultrasonic energy to the slurry of at least 200        kWh/t continuously by the sonication probe at a frequency range        of 19 to 100 kHz;    -   (f) collecting the re-dispersed suspension comprising        microfibrillated cellulose with enhanced tensile strength and/or        viscosity properties from the at least one outlet of the flow        cell in a suitable holding vessel.

In an alternative embodiment the method may comprise a second outlet ofthe flow cell is connected to a second inlet of the tank, therebyproviding for a continuous recirculation loop providing for thecontinuous application of ultrasonic energy to the slurry for a desiredtime period and/or total energy input range. Thus, the method may bepracticed in the alternative as a single pass through the flow cellcomprising at least one sonication probe or may be practiced in acontinuous manner by recirculating a slurry comprising microfibrillatedcellulose or a slurry comprising microfibrillated cellulose and at leastone inorganic particulate material through the above-describedrecirculation loop comprising the flow cell comprising at least onesonication probe. In a preferred embodiment, the dispersing liquid iswater.

In an embodiment, the cumulative ultrasonic energy input may be adjustedto at least about 200 kWh/t, at least about 300 kWh/t, at least about400 kWh/t, at least about 500 kWh/t, at least about 600 kWh/t, at leastabout 700 kWh/t, at least about 800 kWh/t, at least about 900 kWh/t, atleast about 1,000 kWh/t, at least about 1,100 kWh/t, at least about1,200 kWh/t, at least about 1,300 kWh/t, at least about 1,400 kWh/t, atleast about 1,500 kWh/t, at least about 1,600 kWh/t, at least about1,700 kWh/t, at least about 1,750 kWh/t, at least about 1,800 kWh/t, atleast about 1,900 kWh/t, at least about 2,000 kWh/t, at least about2,100 kWh/t, at least about 2,200 kWh/t, at least about 2,300 kWh/t, atleast about 2,400 kWh/t, at least about 2,500 kWh/t, at least about3,000 kWh/t, at least about 3,500 kWh/t, at least about 4,000 kWh/t, atleast about 4,500 kWh/t, at least about 5,000 kWh/t, at least about5,500 kWh/t, at least about 6,000 kWh/t, at least about 6,500 kWh/t, atleast about 7,000 kWh/t, at least about 7,500 kWh/t, at least about8,000 kWh/t, at least about 8,500 kWh/t, at least about 9,000 kWh/t, atleast about 9,500 kWh/t, or at least about 10,000 kWh/t.

In an embodiment, the flow cell comprises a cooling jacket formaintaining a temperature of the suspension of microfibrillatedcellulose in the range of about 1° C. to about 80° C., 20° C. to about50° C., or at room temperature, or about 20° C.

In an embodiment, the flow cell comprises an adjustable valve at thesecond outlet to create back pressure of the recirculated liquid of fromabout 0 to about 10 bar, or about 0 to about 4 bar,

In an embodiment, flow cell further comprises one or more boosters tomechanically increase or decrease the amplitude of the at least onesonication probe. The person skilled in the art will understand howboosters may be used to adjust the amplitude of the ultrasonic energyemitted from the sonication probe.

In an embodiment, the liquid composition, preferably an aqueous slurry,is at least about 0.5 to about 5%, or at least about 0.5 to about 6%fibre solids, or at least about 0.5 to about 7, or at least about 0.5 toabout 8%, or at least about 0.5 to about 9%, or at least about 0.5 toabout 10%, or about 1.5% fibre solids, or about 1.6% fibre solids, orabout 1.7% fibre solids, or about 1.8% fibre solids, or about 1.9% fibresolids, or about 2% fibre solids, or about 2.5% fibre solids, or about3% fibre solids, or about 3.5% fibre solids, or about 4% fibre solids,or about 4.5, or about 5% fibre solids, or about 6% fibre solids, orabout 7% fibre solids, or about 8% fibre solids, or about 9% fibresolids %, or about 10% fibre solids.

In some embodiments, the microfibrillated cellulose composition ispelletized.

In other embodiments, the microfibrillated cellulose compositioncomprising inorganic particulate material is pelletized.

In an embodiment, the ultrasonic energy is applied for about 1 to about120 minutes, or about 30 minutes, or about 45 minutes, or about 60minutes, or about 75 minutes, or about 90 minutes, or about 120 minutes.

In an embodiment, the recirculation loop further comprises a high shearmixer.

The person skilled in the art will understand that improvements intensile strength of the suspension of microfibrillated cellulose ormicrofibrillated cellulose and inorganic particulate material may bedemonstrated by the FLT index previously described in thisspecification.

In an embodiment, the improvement in FLT index in suspensions ofmicrofibrillated cellulose or microfibrillated cellulose and inorganicparticulate material made by the methods described in this specificationemploying ultrasonic treatment of such suspensions compared tosuspensions of microfibrillated cellulose or microfibrillated celluloseand inorganic particulate material which were not made by the methodsdescribed in this specification employing ultrasonic treatment of suchsuspensions. FLT indices of 7.5 Nm/g or more, of 7.5 Nm/g or more, of 8Nm/g or more, of 8.5 Nm/g or more, of 9 Nm/g or more, of 9.5 Nm/g ormore, of 10 Nm/g or more, of 10.5 Nm/g or more, of 11 Nm/g or more, of11.5 Nm/g or more, of 12 Nm/g or more, of 12.5 Nm/g or more, of 13 Nm/gor more, of 13.5 Nm/g or more, of 14 Nm/g or more, of 14.5 Nm/g or more,or of 15 Nm/g or more are achievable through the methods disclosed inthe specification.

In an embodiment improvements in FLT index of about 5%, about 6%, about7%, about 7.5%, about 8%, about 9%, about 10%, about 12.5%, about 15% orabout 20% or more may be achieved.

In an embodiment improvements in viscosity of about 5%, about 6%, about7%, about 7.5%, about 8%, about 9%, about 10%, about 12.5%, about 15% orabout 20% or more may be achieved compared to suspensions ofmicrofibrillated cellulose or microfibrillated cellulose and inorganicparticulate material produced without the application of ultrasonicenergy treatment to the slurry or suspension.

In an embodiment, the liquid composition comprising microfibrillationcellulose is recirculated for about 30 to about 120 minutes, or about 30to about 90 minutes, or about 30 to about 75 minutes, or about 30 toabout 60 minutes, or about 30 to about 45 minutes, or about 30 minutes.

In an aspect of this invention, a re-dispersed microfibrillatedcellulose suspension is produced by the processes disclosed in thisspecification.

In an embodiment, the method further comprises one or more of high shearmixing, homogenization and refining either before or after thesonication step.

In an embodiment, the inventors have invented a method for re-dispersingdewatered, partially dried or essentially dried microfibrillatedcellulose, the method comprising the steps of:

-   -   (a) adding a quantity of a suitable dispersing liquid to a        closed tank, wherein the tank comprises an inlet and an outlet        connected to a pump comprising a first inlet and a first outlet,        and a flow cell comprising a second inlet and a second outlet,        and further comprising at least one sonication probe        (sonotrode), thereby forming a closed recirculation loop;    -   (b) adding a quantity of dewatered, partially dried or        essentially dried microfibrillated cellulose to the tank in        sufficient quantity to yield a liquid composition of        microfibrillated cellulose at a desired solids concentration;    -   wherein the liquid composition comprising microfibrillated        cellulose of step (b) is continuously recirculated through the        recirculation loop;    -   (c) applying ultrasonic energy of at least 200 kWh/t        intermittently or continuously by the sonotrode at a frequency        range of 20 to 100 Hz to the liquid composition of        microfibrillated cellulose,

thereby forming a re-dispersed suspension comprising microfibrillatedcellulose with enhanced tensile strength and/or enhanced viscosityproperties.

In an additional embodiment, the foregoing method for re-dispersingdewatered, partially dried or essentially dried microfibrillatedcellulose composition may include at least one inorganic particulatematerial. The at least one inorganic particulate material may be addedto the liquid composition of microfibrillated cellulose or may bepresent due to the co-processing of cellulose fibres with inorganicparticulate material in the fibrillation process as previously describedin this specification.

In a preferred embodiment of the process, the liquid composition ofmicrofibrillated cellulose is an aqueous suspension.

The sonification step of the process may be carried out with at leastone sonication probe (sonotrode) contained within a flow cell comprisingforming part of a closed recirculation loop. The closed recirculationloop comprises a closed tank for adding a suitable dispersing liquid,preferably water. The tank is connected to an inlet to a suitable pump.An outlet of the pump is connected to an inlet to the flow cellcomprising the at least one sonotrode. The outlet of the flow cell isconnected by a tube to a second inlet to the closed mixing tank, therebycreating a recirculating loop for recirculation of the liquidcomposition comprising microfibrillated cellulose and optionally atleast one inorganic particulate material.

In certain embodiments, the liquid composition of microfibrillatedcellulose or microfibrillated cellulose and inorganic particulatematerial may contain other optional additives. The optional additivescould be, for example, a retention aid, or other additives used inpapermaking compositions, for example, a sizing agent which may be, forexample, a long chain alkylketene dimer, a wax emulsion or a succinicacid derivative. The composition may also contain dye and/or an opticalbrightening agent. The composition may also comprise dry and wetstrength aids such as, for example, starch or epichlorhydrin copolymers.Other optional additives include dispersant, biocide, suspending aids,salt(s) and other additives, for example, starch orcarboxymethylcellulose or polymers, which may facilitate the interactionof mineral particles and fibres during or after grinding.

The liquid composition of microfibrillated cellulose, an optionally atleast one or more inorganic particulate material, is continuouslyrecirculated through the recirculation loop. During recirculation of theliquid composition of microfibrillated cellulose, and optionally atleast one or more inorganic particulate material, ultrasonic energy isapplied through an ultrasonication device. In a preferred embodiment,the ultrasonication device is a sonotrode is well known in the art.Exemplary sonotrodes are available from, for example, HielscherUltrasonics GmbH (Oderstr. 53 D-14513 Teltow, Germany and 530 RingwoodAve. Lembo & Gray Bldg. Wanaque, N.J. 07465, USA).

Ultrasonic energy may be applied continuously or intermittently by thesonication probe (sonotrode) housed within the flow cell. Ultrasonicenergy may be applied in an cumulative amount of at least about 200kWh/t, at least about 300 kWh/t, at least about 400 kWh/t, at leastabout 500 kWh/t, at least about 600 kWh/t, at least about 700 kWh/t, atleast about 800 kWh/t, at least about 900 kWh/t, at least about 1,000kWh/t, at least about 1,100 kWh/t, at least about 1,200 kWh/t, at leastabout 1,300 kWh/t, at least about 1,400 kWh/t, at least about 1,500kWh/t, at least about 1,600 kWh/t, at least about 1,700 kWh/t, at leastabout 1,750 kWh/t, at least about 1,800 kWh/t, at least about 1,900kWh/t, at least about 2,000 kWh/t, at least about 2,100 kWh/t, at leastabout 2,200 kWh/t, at least about 2,300 kWh/t, at least about 2,400kWh/t, at least about 2,500 kWh/t, at least about 3,000 kWh/t, at leastabout 3,500 kWh/t, at least about 4,000 kWh/t, at least about 4,500kWh/t, at least about 5,000 kWh/t, at least about 5,500 kWh/t, at leastabout 6,000 kWh/t, at least about 6,500 kWh/t, at least about 7,000kWh/t, at least about 7,500 kWh/t, at least about 8,000 kWh/t, at leastabout 8,500 kWh/t, at least about 9,000 kWh/t, at least about 9,500kWh/t, or at least about 10,000 kWh/t.

In an embodiment, the flow cell comprises a cooling jacket formaintaining a temperature of the suspension of microfibrillatedcellulose in the range of about 1° C. to about 80° C., or about 20° C.to about 50°, or at room temperature, or preferably about 20° C.

In an embodiment, the flow cell comprises an adjustable valve at thesecond outlet to create back pressure of the recirculated liquid of fromabout 0 to about 10 bar., or about 0 to 4 bar, preferably about 3 bar.

In an embodiment, flow cell further comprises one or more boosters tomechanically increase or decrease the amplitude of the at least onesonication probe. The person skilled in the art will understand howboosters may be used to adjust the amplitude of the ultrasonic energyemitted from the sonication probe.

In an embodiment, the liquid composition, preferably an aqueous slurry,is at least about 0.5% to about 5%, or at least about 0.5% to about 6%fibre solids, or at least about 0.5% to about 7, or at least about 0.5to about 8%, or at least about 0.5 to about 9%, or at least about 0.5%to about 10%, or about 1.5% fibre solids, or about 1.6% fibre solids, orabout 1.7% fibre solids, or about 1.8% fibre solids, or about 1.9% fibresolids, or about 2% fibre solids, or about 2.5% fibre solids, or about3% fibre solids, or about 3.5% fibre solids, or about 4% fibre solids,or about 4.5, or about 5% fibre solids, or about 6% fibre solids, orabout 7% fibre solids, or about 8% fibre solids, or about 9% fibresolids %, or about 10% fibre solids.

In an embodiment, ultrasonication is advantageously used to re-dispersepreviously dewatered, partially dried or essentially dried compositionsof microfibrillated cellulose or compositions of microfibrillatedcellulose and inorganic particulate material. The dewatered, partiallydried or essentially dried compositions of microfibrillated cellulose orcompositions of microfibrillated cellulose and inorganic particulatematerial may be pelletized after dewatering and drying. Such dewatered,partially dried or dried, and optionally pelletized, compositions ofmicrofibrillated cellulose or compositions of microfibrillated celluloseand inorganic particulate material are re-suspended with the aid ofultrasonication devices of the types described in this specification.

In an embodiment, the ultrasonic energy is applied for about 1 to about120 minutes, or about 30 minutes, or about 45 minutes, or about 60minutes, or about 75 minutes, or about 90 minutes, or about 120 minutes.

The person skilled in the art will understand that improvements intensile strength of the suspension of microfibrillated cellulose ormicrofibrillated cellulose and inorganic particulate material may bedemonstrated by the FLT index previously described in thisspecification.

In an embodiment, the improvement in FLT index in suspensions ofmicrofibrillated cellulose or microfibrillated cellulose and inorganicparticulate material made by the methods described in this specificationemploying ultrasonic treatment of such suspensions compared tosuspensions of microfibrillated cellulose or microfibrillated celluloseand inorganic particulate material which were not made by the methodsdescribed in this specification employing ultrasonic treatment of suchsuspensions. FLT indices of 7.5 Nm/g or more, of 7.5 Nm/g or more, of 8Nm/g or more, of 8.5 Nm/g or more, of 9 Nm/g or more, of 9.5 Nm/g ormore, of 10 Nm/g or more, of 10.5 Nm/g or more, of 11 Nm/g or more, of11.5 Nm/g or more, of 12 Nm/g or more, of 12.5 Nm/g or more, of 13 Nm/gor more, of 13.5 Nm/g or more, of 14 Nm/g or more, of 14.5 Nm/g or more,or of 15 Nm/g or more, are achievable through the methods disclosed inthe specification.

In an embodiment of the present invention, the tensile strength of theaqueous suspension comprising microfibrillated cellulose and inorganicparticulate material with enhanced viscosity and tensile strengthproperties is increased by at least 5%, at least 10%, at least 20%, atleast 50%, at least 100% or at least 200% over the aqueous suspensioncomprising microfibrillated cellulose and inorganic particulate materialnot subject to sonication.

In an embodiment of the present invention, the viscosity of the aqueoussuspension comprising microfibrillated cellulose and inorganicparticulate material with enhanced viscosity and tensile strengthproperties is increased by at least 5%, at least by 10% or at least by20%, by at least 50%, by at least 100% over the aqueous suspensioncomprising microfibrillated cellulose and inorganic particulate materialnot subject to sonication.

In an embodiment of the present invention, the aqueous suspensioncomprising microfibrillated cellulose and inorganic particulate materialis subject to sonication for at least 30 seconds, at least 1 minute, atleast 2 minutes, at least 5 minutes, at least 10 minutes and at least 20minutes or longer. The length of time may be determined by one ofordinary skill in the art based on the teachings of this specification.

In an embodiment of the present invention, the aqueous suspensioncomprising microfibrillated cellulose and inorganic particulate materialis subject to sonication at an energy compensation rate of up to 1000kwh per tonne of dried fibrils, up to 2000 kwh per tonne, 2500 kwh pertonne of dried fibrils, up to 5000 kwh per tonne of dried fibrils and upto 10000 kwh per tonne of dried fibrils. As set forth in the Examples ofthis application, sonication was found to be more effective forre-dispersing and de-agglomerating microfibrillated cellulose orcompositions of microfibrillated cellulose and inorganic particulatematerial that had been dewatered, partially dried, or essentially driedand pelletized. In other embodiments, re-dispersion of slurries ofslurries of microfibrillated cellulose or compositions ofmicrofibrillated cellulose and inorganic particulate material throughsonication yielded improvements in product quality at energy inputsbetween 200 kWh/t and 10,000 kWh/t, especially between 1000 kWh/t and2000 kWh/t.

In an embodiment, sonication of mineral free microfibrillated cellulose(e.g., birch) produced using the a pilot scale stirred media detritor(Supermill) yielded products with comparable specifications tomicrofibrillated cellulose made by grinding processes in, for example aSupermill, followed by a homogenization step when sonicated at about1500 kWh/t.

In certain embodiments, the aqueous suspension comprisingmicrofibrillated cellulose and inorganic particulate material may besonicated by running the sonicator in continuous mode or in pulse modeor a combination of both. That is, where alternating long pulses andshort pulses are performed as desired patterns or at random.

In preferred embodiments, the aqueous suspension comprisingmicrofibrillated cellulose and inorganic particulate material may beformed into a semi (partially)-dry product prior to sonication. A beltpressed cake is one example of a semi-dried product suitable for use inthe present invention. In certain embodiments, the belt press cake maybe further subjected to treatment in an air swept dryer and mill, suchas an Atritor dryer. Often converting the product to a semi-dry productis done, for example, for ease of handling and/or transport. In theevent of using a semi-dried product as a starting material, sonicationnot only provides enhanced physical properties to the material but alsoaids in disbursement of the material into solution in a process referredto as rewetting.

The sonication of the aqueous suspension comprising microfibrillatedcellulose and inorganic particulate material is not limited to anyparticular or specific sonication parameters as a change on oneparameter may compensate for a change in another parameter, withinphysical and practical limits of the equipment and material beingsonicated. For example, lengthening sonication time may compensate atleast partly for using a reduced amplitude.

In preferred embodiments, the sonication is performed at an amplitude ofup to 60%, up to 80%, up to 100% and up to 200% or more, to the physicallimitations of the sonicator used. Said upper physical limits ofamplitude of a particular device used are known to one of ordinary skillin the art.

The fibrous substrate comprising cellulose may be in the form of a pulp,for example, a chemical pulp, or a chemithermomechanical pulp, or amechanical pulp, or a recycled pulp, or a paper broke pulp, or apapermill waste stream, or waste from a papermill, or combinationsthereof.

The inorganic particulate material may be an alkaline earth metalcarbonate or sulphate, such as calcium carbonate, magnesium carbonate,dolomite, gypsum, a hydrous kandite clay such as kaolin, halloysite orball clay, an anhydrous (calcined) kandite clay such as metakaolin orfully calcined kaolin, talc, mica, perlite or diatomaceous earth, orcombinations thereof. In a preferred embodiment, the inorganicparticulate material is an alkaline earth metal carbonate, for example,calcium carbonate or kaolin or a combination thereof.

The grinding vessel may be a tower mill or a stirred media detritor.

In an embodiment, the aqueous suspension comprising microfibrillatedcellulose and inorganic particulate material with enhanced viscosity andtensile strength properties obtained by the method of the presentinvention is suitable for use in a method of making paper or coatingpaper and is suitable for other use in other processes and materialswhere microfibrillated cellulose is typically used, examples of whichare detailed below in the section entitled “Other Uses.”

In another aspect of the invention, the cellulose suspension may beproduced without the use of an inorganic particulate material. In theseinstances, a grinding media, as discussed above and below, may be usedin place of the inorganic particulate material. In this regard, theultrasonication of the cellulose suspension of the present inventioncomprises producing an aqueous suspension comprising microfibrillatedcellulose with enhanced viscosity and tensile strength properties, themethod comprising a step of microfibrillating a fibrous substratecomprising cellulose in an aqueous environment to produce an aqueoussuspension comprising microfibrillated cellulose, and further comprisingsubjecting the aqueous suspension comprising microfibrillated celluloseto sonication to produce the aqueous suspension comprisingmicrofibrillated cellulose with enhanced viscosity and tensile strengthproperties. The microfibrillating step may comprise grinding the fibroussubstrate comprising cellulose in the presence of a grinding media, thegrinding media having a desired particle size. The grinding media may bepartially or completely removed after the microfibrillating step.

Ultrasonication of the aqueous suspension comprising microfibrillatedcellulose may be conducted with an ultrasonic probe or ultrasonic waterbath, an ultrasonic homogenizer, an ultrasonic foil or an ultrasonichorn. The use of such devices is known to one of ordinary skill in theart.

Such probes are known to one of ordinary skill in the art. In view ofthe teachings of this specification, one of ordinary skill in the artwill be able to discern the appropriate parameters without undueexperimentation.

In an embodiment of the present invention, the methods of the presentinvention may further comprise one or more of high shear mixing,homogenisation or refining either before or after the sonication step,all of which are known by one of ordinary skill in the art and may beincorporated into the methods of the present invention without undueexperimentation in view of the teachings of this specification.

In an embodiment of the present invention, the tensile strength of theaqueous suspension comprising microfibrillated cellulose with enhancedviscosity and tensile strength properties is increased by at least 5%,at least 10%, at least 20%, at least 50%, at least 100% or at least 200%over the aqueous suspension comprising microfibrillated cellulose andinorganic particulate material not subject to sonication.

In an embodiment of the present invention, the viscosity of the aqueoussuspension comprising microfibrillated cellulose with enhanced viscosityand tensile strength properties is increased by at least 5%, at least by10% or at least by 20%, by at least 50%, by at least 100% over theaqueous suspension comprising microfibrillated cellulose and inorganicparticulate material not subject to sonication.

In an embodiment of the present invention, the aqueous suspensioncomprising microfibrillated cellulose is subject to sonication for atleast 30 seconds, at least 1 minute, at least 2 minutes, at least 3minutes, at least 4 minutes, at least 5 minutes, at least 10 minutes andat least 20 minutes or longer. The length of time may be determined byone of ordinary skill in the art based on the teachings of thisspecification.

In an embodiment of the present invention, the aqueous suspensioncomprising microfibrillated cellulose is subject to sonication at anenergy compensation rate of up to 1000 kwh per tonne of dried fibrils,up to 1500 kwh per tonne, up to 2000 kwh per tonne, up to 2500 kwh pertonne of dried fibrils, up to 5000 kwh per tonne of dried fibrils and upto 10000 kwh per tonne of dried fibrils.

The aqueous suspension comprising microfibrillated cellulose and,optionally inorganic particulate material, may be sonicated by runningthe sonicator in continuous mode or in pulse mode or a combination ofboth. That is, where alternating long pulses and short pulses areperformed as desired patterns or at random.

The aqueous suspension comprising microfibrillated cellulose and,optionally inorganic particulate material, may be formed into a semi(partially)-dry product prior to sonication. A belt pressed cake is oneexample of a semi-dried product suitable for use in the presentinvention. Another embodiment is a belt pressed cake followed by furtherdrying in an air swept mill such as an Atritor dryer mill. Oftenconverting the product to a semi-dry product is done, for example, forease of handling and/or transport. In the event of using a semi-driedproduct as a starting material, sonication not only provides enhancedphysical properties to the material but also aids in disbursement of thematerial into solution or suspension.

The sonication of the aqueous suspension comprising microfibrillatedcellulose and, optionally inorganic particulate material, is not limitedto any particular or specific sonication parameters as a change on oneparameter may compensate for a change in another parameter, withinphysical and practical limits. For example, lengthening sonication timemay compensate at least partly for a reduced amplitude.

In preferred embodiments, the sonication is performed at an amplitude ofup to 60%, up to 80%, up to 100% and up to 200% or more, to the physicallimitations of the sonicator used. Said upper physical limits ofamplitude of a particular device used are known to one of ordinary skillin the art.

The fibrous substrate comprising cellulose may be in the form of a pulp,for example, a chemical pulp, or a chemithermomechanical pulp, or amechanical pulp, or a recycled pulp, or a paper broke pulp, or apapermill waste stream, or waste from a papermill, or combinationsthereof.

In an embodiment, the aqueous suspension comprising microfibrillatedcellulose and, optionally, inorganic particulate material with enhancedviscosity and tensile strength properties obtained by the method of thepresent invention is suitable for use in a method of making paper orcoating paper and is suitable for other use in other processes andmaterials where microfibrillated cellulose is typically used and issuitable for other use in other processes and materials wheremicrofibrillated cellulose is typically used, examples of which aredetailed below in the section entitled “Other Uses.”

Paper Products and Processes for Preparing Same

The aqueous suspension comprising microfibrillated cellulose andinorganic particulate material can be incorporated in papermakingcompositions, which in turn can be used to prepare paper products. Theterm paper product, as used in connection with the present invention,should be understood to mean all forms of paper, including board suchas, for example, white-lined board and linerboard, cardboard,paperboard, coated board, and the like. There are numerous types ofpaper, coated or uncoated, which may be made according to the presentinvention, including paper suitable for books, magazines, newspapers andthe like, and office papers. The paper may be calendered or supercalendered as appropriate; for example super calendered magazine paperfor rotogravure and offset printing may be made according to the presentmethods. Paper suitable for light weight coating (LWC), medium weightcoating (MWC) or machine finished pigmentisation (MFP) may also be madeaccording to the present methods.

Coated paper and board having barrier properties suitable for foodpackaging and the like may also be made according to the presentmethods. In a typical papermaking process, a cellulose-containing pulpis prepared by any suitable chemical or mechanical treatment, orcombination thereof, which are well known in the art. The pulp may bederived from any suitable source such as wood, grasses (e.g., sugarcane,bamboo) or rags (e.g., textile waste, cotton, hemp or flax). The pulpmay be bleached in accordance with processes which are well known tothose skilled in the art and those processes suitable for use in thepresent invention will be readily evident. The bleached cellulose pulpmay be beaten, refined, or both, to a predetermined freeness (reportedin the art as Canadian standard freeness (CSF) in cm³). A suitable paperstock is then prepared from the bleached and beaten pulp.

The papermaking composition of the present invention typicallycomprises, in addition to the aqueous suspension of microfibrillatedcellulose and inorganic particulate material, paper stock and otherconventional additives known in the art. The papermaking composition ofthe present invention may comprise up to about 50% by weight inorganicparticulate material derived from the aqueous suspension comprisingmicrofibrillated cellulose and inorganic particulate material based onthe total dry contents of the papermaking composition. For example, thepapermaking composition may comprise at least about 2% by weight, or atleast about 5% by weight, or at least about 10% by weight, or at leastabout 15% by weight, or at least about 20% by weight, or at least about25% by weight, or at least about 30% by weight, or at least about 35% byweight, or at least about 40% by weight, or at least about 45% byweight, or at least about 50% by weight, or at least about 60% byweight, or at least about 70% by weight, or at least about 80% by weightof inorganic particulate material derived from the aqueous suspensioncomprising microfibrillated cellulose and inorganic particulate materialbased on the total dry contents of the papermaking composition. Themicrofibrillated cellulose material may have a fibre steepness ofgreater than about 10, for examples, from about 20 to about 50, or fromabout 25 to about 40, or from about 25 to 35, or from about 30 to about40. The papermaking composition may also contain a non-ionic, cationicor an anionic retention aid or microparticle retention system in anamount in the range from about 0.1 to 2% by weight, based on the dryweight of the aqueous suspension comprising microfibrillated celluloseand inorganic particulate material. It may also contain a sizing agentwhich may be, for example, a long chain alkylketene dimer, a waxemulsion or a succinic acid derivative. The composition may also containdye and/or an optical brightening agent. The composition may alsocomprise dry and wet strength aids such as, for example, starch orepichlorhydrin copolymers.

In one embodiment, the present invention is directed to a process formaking a paper product comprising: (i) obtaining or preparing a fibroussubstrate comprising cellulose in the form of a pulp suitable for makinga paper product; (ii) preparing a papermaking composition from the pulpin step (i), the aqueous suspension of this invention comprisingmicrofibrillated cellulose and inorganic particulate material, and otheroptional additives (such as, for example, a retention aid, and otheradditives such as those described above); and (iii) forming a paperproduct from said papermaking composition. As noted above, the step offorming a pulp may take place in the grinder vessel or homogenizer byaddition of the fibrous substrate comprising cellulose in a dry state,for example, in the form of a dry paper broke or waste, directly to thegrinder vessel. The aqueous environment in the grinder vessel orhomogenizer will then facilitate the formation of a pulp.

In one embodiment, an additional filler component (i.e., a fillercomponent other than the inorganic particulate material which isco-ground with the fibrous substrate comprising cellulose) can be addedto the papermaking composition prepared in step (ii). Exemplary fillercomponents are PCC, GCC, kaolin, or mixtures thereof. An exemplary PCCis scalenohedral PCC. In an embodiment, the weight ratio of theinorganic particulate material to the additional filler component in thepapermaking composition is from about 1:1 to about 1:30, for example,from about 1:1 to about 1:20, for example, from about 1:1 to about 1:15,for example from about 1:1 to about 1:10, for example from about 1:1 toabout 1:7, for example, from about 1:3 to about 1:6, or about 1:1, orabout 1:2, or about 1:3, or about 1:4, or about 1:5. Paper products madefrom such papermaking compositions may exhibit greater strength comparedto paper products comprising only inorganic particulate material, suchas for example PCC, as filler. Paper products made from such papermakingcompositions may exhibit greater strength compared to a paper product inwhich inorganic particulate material and a fibrous substrate comprisingcellulose are prepared (e.g., ground) separately and are admixed to forma paper making composition. Equally, paper products prepared from apapermaking composition according to the present invention may exhibit astrength which is comparable to paper products comprising less inorganicparticulate material. In other words, paper products can be preparedfrom a paper making composition according to the present at higherfiller loadings without loss of strength.

The steps in the formation of a final paper product from a papermakingcomposition are conventional and well known in the art and generallycomprise the formation of paper sheets having a targeted basis weight,depending on the type of paper being made.

Additional economic benefits can be achieved through the methods of thepresent invention in that the cellulose substrate for making the aqueoussuspension can be derived from the same cellulose pulp formed for makingthe papermaking composition and the final paper product. As such, and inaccordance with an aspect of the invention described above, the presentinvention is directed to a an integrated process for making a paperproduct comprising: (i) obtaining or preparing a fibrous substratecomprising cellulose in the form of a pulp suitable for making a paperproduct; (ii) microfibrillating a portion of said fibrous substratecomprising cellulose in accordance with the first aspect of theinvention to prepare an aqueous suspension comprising microfibrillatedcellulose and inorganic particulate material; (iii) preparing apapermaking composition from the pulp in step (i), the aqueoussuspension prepared in step (ii), and other optional additives; and iv)forming a paper product from said papermaking composition.

Thus, since the cellulose substrate for preparing the aqueous suspensionhas already been prepared for the purpose of making the papermakingcompositions, the step of forming the aqueous suspension does notnecessarily require a separate step of preparing the fibrous substratecomprising cellulose.

Paper products prepared using the aqueous suspension of the presentinvention have surprisingly been found to exhibit improved physical andmechanical properties whilst at the same time enabling the inorganicparticulate material to be incorporated at relatively high loadinglevels. Thus, improved papers can be prepared at relatively less cost.For example, paper products prepared from papermaking compositionscomprising the aqueous suspension of the present invention have beenfound to exhibit improved retention of the inorganic particulatematerial filler compared to paper products which do not contain anymicrofibrillated cellulose. Paper products prepared from papermakingcompositions comprising the aqueous suspension of the present inventionhave also been found to exhibit improved burst strength and tensilestrength. Further, the incorporation of the microfibrillated cellulosehas been found to reduce porosity compared to paper comprising the sameamount of filler but no microfibrillated cellulose. This is advantageoussince high filler loading levels are generally associated withrelatively high values of porosity and are detrimental to printability.

Paper Coating Composition and Coating Process

The aqueous suspension of the present invention can be used as a coatingcomposition without the addition of further additives. However,optionally, a small amount of thickener such as carboxymethylcelluloseor alkali-swellable acrylic thickeners or associated thickeners may beadded.

The coating composition according to the present invention may containone or more optional additional components, if desired. Such additionalcomponents, where present, are suitably selected from known additivesfor paper coating compositions. Some of these optional additives mayprovide more than one function in the coating composition. Examples ofknown classes of optional additives are as follows:

(a) one or more additional pigments: the compositions described hereincan be used as sole pigments in the paper coating compositions, or maybe used in conjunction with one another or with other known pigments,such as, for example, calcium sulphate, satin white, and so-called“plastic pigment”. When a mixture of pigments is used, the total pigmentsolids content is preferably present in the composition in an amount ofat least about 75 wt. % of the total weight of the dry components of thecoating composition;

(b) one or more binding or co-binding agents: for example, latex, whichmay, optionally, be carboxylated, including: a styrene-butadiene rubberlatex; an acrylic polymer latex; a polyvinyl acetate latex; or a styreneacrylic copolymer latex, starch derivatives, sodium carboxymethylcellulose, polyvinyl alcohol, and proteins;

(c) one or more cross linkers: for example, in levels of up to about 5%by weight; e.g., glyoxals, melamine formaldehyde resins, ammoniumzirconium carbonates; one or more dry or wet pick improvement additives:e.g., in levels up to about 2% by weight, e.g., melamine resin,polyethylene emulsions, urea formaldehyde, melamine formaldehyde,polyamide, calcium stearate, styrene maleic anhydride and others; one ormore dry or wet rub improvement and abrasion resistance additives: e.g.,in levels up to about 2% by weight, e.g., glyoxal based resins, oxidisedpolyethylenes, melamine resins, urea formaldehyde, melamineformaldehyde, polyethylene wax, calcium stearate and others; one or morewater resistance additives: e.g., in levels up to about 2% by weight,e.g., oxidised polyethylenes, ketone resin, anionic latex, polyurethane,SMA, glyoxals, melamine resin, urea formaldehyde, melamine formaldehyde,polyamide, stearates and other materials commercially available for thisfunction;

(d) one or more water retention aids: for example, in levels up to about2% by weight, e.g., sodium carboxymethyl cellulose, hydroxyethylcellulose, PVOH (polyvinyl alcohol), starches, proteins, polyacrylates,gums, alginates, polyacrylamide bentonite and other commerciallyavailable products sold for such applications;

(e) one or more viscosity modifiers and/or thickeners: for example, inlevels up to about 2% by weight; e.g., acrylic associative thickeners,polyacrylates, emulsion copolymers, dicyanamide, triols, polyoxyethyleneether, urea, sulphated castor oil, polyvinyl pyrrolidone, CMC(carboxymethyl celluloses, for example sodium carboxymethylcellulose),sodium alginate, xanthan gum, sodium silicate, acrylic acid copolymers,HMC (hydroxymethylcelluloses), HEC (hydroxyethylcelluloses) and others;

(f) one or more lubricity/calendering aids: for example, in levels up toabout 2% by weight, e.g., calcium stearate, ammonium stearate, zincstearate, wax emulsions, waxes, alkyl ketene dimer, glycols; one or moregloss-ink hold-out additives: e.g., in levels up to about 2% by weight,e.g., oxidised polyethylenes, polyethylene emulsions, waxes, casein,guar gum, CMC, HMC, calcium stearate, ammonium stearate, sodium alginateand others;

(g) one or more dispersants: the dispersant is a chemical additivecapable, when present in a sufficient amount, of acting on the particlesof the particulate inorganic material to prevent or effectively restrictflocculation or agglomeration of the particles to a desired extent,according to normal processing requirements. The dispersant may bepresent in levels up to about 1% by weight, and includes, for example,polyelectrolytes such as polyacrylates and copolymers containingpolyacrylate species, especially polyacrylate salts (e.g., sodium andaluminium optionally with a group II metal salt), sodiumhexametaphosphates, non-ionic polyol, polyphosphoric acid, condensedsodium phosphate, non-ionic surfactants, alkanolamine and other reagentscommonly used for this function. The dispersant may, for example, beselected from conventional dispersant materials commonly used in theprocessing and grinding of inorganic particulate materials. Suchdispersants will be well recognized by those skilled in this art. Theyare generally water-soluble salts capable of supplying anionic specieswhich in their effective amounts can adsorb on the surface of theinorganic particles and thereby inhibit aggregation of the particles.The unsolvated salts suitably include alkali metal cations such assodium. Solvation may in some cases be assisted by making the aqueoussuspension slightly alkaline. Examples of suitable dispersants include:water soluble condensed phosphates, e.g., polymetaphosphate salts[general form of the sodium salts: (NaPO₃)_(x)] such as tetrasodiummetaphosphate or so-called “sodium hexametaphosphate” (Graham's salt);water-soluble salts of polysilicic acids; polyelectrolytes; salts ofhomopolymers or copolymers of acrylic acid or methacrylic acid, or saltsof polymers of other derivatives of acrylic acid, suitably having aweight average molecular mass of less than about 20,000. Sodiumhexametaphosphate and sodium polyacrylate, the latter suitably having aweight average molecular mass in the range of about 1,500 to about10,000, are especially preferred;

(h) one or more antifoamers and defoamers: for example, in levels up toabout 1% by weight, e.g., blends of surfactants, tributyl phosphate,fatty polyoxyethylene esters plus fatty alcohols, fatty acid soaps,silicone emulsions and other silicone containing compositions, waxes andinorganic particulates in mineral oil, blends of emulsified hydrocarbonsand other compounds sold commercially to carry out this function;

(i) one or more optical brightening agents (OBA) and fluorescentwhitening agents (FWA): for example, in levels up to about 1% by weight,e.g., stilbene derivatives;

(j) one or more dyes: for example, in levels up to about 0.5% by weight;

(k) one or more biocides/spoilage control agents: for example, in levelsup to about 1% by weight, e.g., oxidizing biocides such as chlorine gas,chlorine dioxide gas, sodium hypochlorite, sodium hypobromite, hydrogen,peroxide, peracetic oxide, ammonium bromide/sodium hypochlorite, ornon-oxidising biocides such as GLUT (Glutaraldehyde, CAS No 90045-36-6),ISO (CIT/MIT) (Isothiazolinone, CAS Np 55956-84-9 & 96118-96-6), ISO(BIT/MIT) (Isothiazolinone), ISO (BIT) (Isothiazolinone, CAS No2634-33-5), DBNPA, BNPD (Bronopol), NaOPP, CARBAMATE, THIONE (Dazomet),EDDM-dimethanol (0-formal), HT-Triazine (N-formal), THPS-tetrakis(0-formal), TMAD-diurea (N-formal), metaborate, sodium dodecylbenenesulphonate, thiocyanate, organosulphur, sodium benzoate and othercompounds sold commercially for this function, e.g., the range ofbiocide polymers sold by Nalco;

(l) one or more levelling and evening aids: for example, in levels up toabout 2% by weight, e.g., non-ionic polyol, polyethylene emulsions,fatty acid, esters and alcohol derivatives, alcohol/ethylene oxide,calcium stearate and other compounds sold commercially for thisfunction;

(m) one or more grease and oil resistance additives: for example, inlevels up to about 2% by weight, e.g., oxidised polyethylenes, latex,SMA (styrene maleic anhydride), polyamide, waxes, alginate, protein,CMC, and HMC.

Any of the above additives and additive types may be used alone or inadmixture with each other and with other additives, if desired.

For all of the above additives, the percentages by weight quoted arebased on the dry weight of inorganic particulate material (100%) presentin the composition. Where the additive is present in a minimum amount,the minimum amount may be about 0.01% by weight based on the dry weightof pigment.

The coating process is carried out using standard techniques which arewell known to the skilled person. The coating process may also involvecalendaring or supercalendering the coated product.

Methods of coating paper and other sheet materials, and apparatus forperforming the methods, are widely published and well known. Such knownmethods and apparatus may conveniently be used for preparing coatedpaper. For example, there is a review of such methods published in Pulpand Paper International, May 1994, page 18 et seq. Sheets may be coatedon the sheet forming machine, i.e., “on-machine” or “off-machine” on acoater or coating machine. Use of high solids compositions is desirablein the coating method because it leaves less water to evaporatesubsequently. However, as is well known in the art, the solids levelshould not be so high that high viscosity and leveling problems areintroduced. The methods of coating may be performed using an apparatuscomprising (i) an application for applying the coating composition tothe material to be coated and (ii) a metering device for ensuring that acorrect level of coating composition is applied. When an excess ofcoating composition is applied to the applicator, the metering device isdownstream of it. Alternatively, the correct amount of coatingcomposition may be applied to the applicator by the metering device,e.g., as a film press. At the points of coating application andmetering, the paper web support ranges from a backing roll, e.g., viaone or two applicators, to nothing (i.e., just tension). The time thecoating is in contact with the paper before the excess is finallyremoved is the dwell time—and this may be short, long or variable.

The coating is usually added by a coating head at a coating station.According to the quality desired, paper grades are uncoated,single-coated, double-coated and even triple-coated. When providing morethan one coat, the initial coat (pre-coat) may have a cheaperformulation and optionally coarser pigment in the coating composition. Acoater that is applying coating on each side of the paper will have twoor four coating heads, depending on the number of coating layers appliedon each side. Most coating heads coat only one side at a time, but someroll coaters (e.g., film presses, gate rolls, and size presses) coatboth sides in one pass.

Examples of known coaters which may be employed include, withoutlimitation, air knife coaters, blade coaters, rod coaters, bar coaters,multi-head coaters, roll coaters, roll or blade coaters, cast coaters,laboratory coaters, gravure coaters, kisscoaters, liquid applicationsystems, reverse roll coaters, curtain coaters, spray coaters andextrusion coaters.

Water may be added to the solids comprising the coating composition togive a concentration of solids which is preferably such that, when thecomposition is coated onto a sheet to a desired target coating weight,the composition has a rheology which is suitable to enable thecomposition to be coated with a pressure (i.e., a blade pressure) ofbetween 1 and 1.5 bar.

Calendering is a well-known process in which paper smoothness and glossis improved and bulk is reduced by passing a coated paper sheet betweencalender nips or rollers one or more times. Usually, elastomer-coatedrolls are employed to give pressing of high solids compositions. Anelevated temperature may be applied. One or more (e.g., up to about 12,or sometimes higher) passes through the nips may be applied.

Coated paper products prepared in accordance with the present inventionand which contain optical brightening agent in the coating may exhibit abrightness as measured according to ISO Standard 11475 which is at least2 units greater, for example at least 3 units greater compared to acoated paper product which does not comprise microfibrillated cellulosewhich has been prepared in accordance with the present invention. Coatedpaper products prepared in accordance with the present invention mayexhibit a Parker Print Surf smoothness measured according to ISOstandard 8971-4 (1992) which is at least 0.5 μm smoother, for example atleast about 0.6 μm smoother, or at least about 0.7 μm smoother comparedto a coated paper product which does not comprise microfibrillatedcellulose which has been prepared in accordance with the presentinvention.

Microfibrillation in the Absence of Grindable Inorganic ParticulateMaterial

In another aspect, the present invention is directed to a method forpreparing an aqueous suspension comprising microfibrillated cellulose,the method comprising a step of microfibrillating a fibrous substratecomprising cellulose in an aqueous environment by grinding in thepresence of a grinding medium which is to be removed after thecompletion of grinding, wherein the grinding is performed in a towermill or a screened grinder, and wherein the grinding is carried out inthe absence of grindable inorganic particulate material.

A grindable inorganic particulate material is a material which would beground in the presence of the grinding medium.

The particulate grinding medium may be of a natural or a syntheticmaterial. The grinding medium may, for example, comprise balls, beads orpellets of any hard mineral, ceramic or metallic material. Suchmaterials may include, for example, alumina, zirconia, zirconiumsilicate, aluminium silicate or the mullite-rich material which isproduced by calcining kaolinitic clay at a temperature in the range offrom about 1300° C. to about 1800° C. For example, in some embodiments aCarbolite® grinding media is preferred. Alternatively, particles ofnatural sand of a suitable particle size may be used.

Generally, the type of and particle size of grinding medium to beselected for use in the invention may be dependent on the properties,such as, e.g., the particle size of, and the chemical composition of,the feed suspension of material to be ground. Preferably, theparticulate grinding medium comprises particles having an averagediameter in the range of from about 0.5 mm to about 6 mm. In oneembodiment, the particles have an average diameter of at least about 3mm.

The grinding medium may comprise particles having a specific gravity ofat least about 2.5. The grinding medium may comprise particles have aspecific gravity of at least about 3, or least about 4, or least about5, or at least about 6.

The grinding medium (or media) may be present in an amount up to about70% by volume of the charge. The grinding media may be present in amountof at least about 10% by volume of the charge, for example, at leastabout 20% by volume of the charge, or at least about 30% by volume ofthe charge, or at least about 40% by volume of the charge, or at leastabout 50% by volume of the charge, or at least about 60% by volume ofthe charge.

The fibrous substrate comprising cellulose may be microfibrillated toobtain microfibrillated cellulose having a d₅₀ ranging from about 5 toμm about 500 μm, as measured by laser light scattering. The fibroussubstrate comprising cellulose may be microfibrillated to obtainmicrofibrillated cellulose having a d₅₀ of equal to or less than about400 μm, for example equal to or less than about 300 μm, or equal to orless than about 200 μm, or equal to or less than about 150 μm, or equalto or less than about 125 μm, or equal to or less than about 100 μm, orequal to or less than about 90 μm, or equal to or less than about 80 μm,or equal to or less than about 70 μm, or equal to or less than about 60μm, or equal to or less than about 50 μm, or equal to or less than about40 μm, or equal to or less than about 30 μm, or equal to or less thanabout 20 μm, or equal to or less than about 10 μm.

The fibrous substrate comprising cellulose may be microfibrillated toobtain microfibrillated cellulose having a modal fibre particle sizeranging from about 0.1-500 μm. The fibrous substrate comprisingcellulose may be microfibrillated in the presence to obtainmicrofibrillated cellulose having a modal fibre particle size of atleast about 0.5 μm, for example at least about 10 μm, or at least about50 μm, or at least about 100 μm, or at least about 150 μm, or at leastabout 200 μm, or at least about 300 μm, or at least about 400 μm.

The fibrous substrate comprising cellulose may be microfibrillated toobtain microfibrillated cellulose having a fibre steepness equal to orgreater than about 10, as measured by Malvern. Fibre steepness (i.e.,the steepness of the particle size distribution of the fibres) isdetermined by the following formula:Steepness=100×(d ₃₀ /d ₇₀)

The microfibrillated cellulose may have a fibre steepness equal to orless than about 100. The microfibrillated cellulose may have a fibresteepness equal to or less than about 75, or equal to or less than about50, or equal to or less than about 40, or equal to or less than about30. The microfibrillated cellulose may have a fibre steepness from about20 to about 50, or from about 25 to about 40, or from about 25 to about35, or from about 30 to about 40.

In one embodiment, the grinding vessel is a tower mill. The tower millmay comprise a quiescent zone above one or more grinding zones. Aquiescent zone is a region located towards the top of the interior of atower mill in which minimal or no grinding takes place and comprisesmicrofibrillated cellulose and inorganic particulate material. Thequiescent zone is a region in which particles of the grinding mediumsediment down into the one or more grinding zones of the tower mill.

The tower mill may comprise a classifier above one or more grindingzones. In an embodiment, the classifier is top mounted and locatedadjacent to a quiescent zone. The classifier may be a hydrocyclone.

The tower mill may comprise a screen above one or more grind zones. Inan embodiment, a screen is located adjacent to a quiescent zone and/or aclassifier. The screen may be sized to separate grinding media from theproduct aqueous suspension comprising microfibrillated cellulose and toenhance grinding media sedimentation.

In an embodiment, the grinding is performed under plug flow conditions.Under plug flow conditions the flow through the tower is such that thereis limited mixing of the grinding materials through the tower. Thismeans that at different points along the length of the tower mill theviscosity of the aqueous environment will vary as the fineness of themicrofibrillated cellulose increases. Thus, in effect, the grindingregion in the tower mill can be considered to comprise one or moregrinding zones which have a characteristic viscosity. A skilled personin the art will understand that there is no sharp boundary betweenadjacent grinding zones with respect to viscosity.

In an embodiment, water is added at the top of the mill proximate to thequiescent zone or the classifier or the screen above one or moregrinding zones to reduce the viscosity of the aqueous suspensioncomprising microfibrillated cellulose at those zones in the mill. Bydiluting the product microfibrillated cellulose at this point in themill it has been found that the prevention of grinding media carry overto the quiescent zone and/or the classifier and/or the screen isimproved. Further, the limited mixing through the tower allows forprocessing at higher solids lower down the tower and dilute at the topwith limited backflow of the dilution water back down the tower into theone or more grinding zones. Any suitable amount of water which iseffective to dilute the viscosity of the product aqueous suspensioncomprising microfibrillated cellulose may be added. The water may beadded continuously during the grinding process, or at regular intervals,or at irregular intervals.

In another embodiment, water may be added to one or more grinding zonesvia one or more water injection points positioned along the length ofthe tower mill, the or each water injection point being located at aposition which corresponds to the one or more grinding zones.Advantageously, the ability to add water at various points along thetower allows for further adjustment of the grinding conditions at any orall positions along the mill.

The tower mill may comprise a vertical impeller shaft equipped with aseries of impeller rotor disks throughout its length. The action of theimpeller rotor disks creates a series of discrete grinding zonesthroughout the mill.

In another embodiment, the grinding is performed in a screened grinder,preferably a stirred media detritor. The screened grinder may compriseone or more screen(s) having a nominal aperture size of at least about250 μm, for example, the one or more screens may have a nominal aperturesize of at least about 300 μm, or at least about 350 μm, or at leastabout 400 μm, or at least about 450 μm, or at least about 500 μm, or atleast about 550 μm, or at least about 600 μm, or at least about 650 μm,or at least about 700 μm, or at least about 750 μm, or at least about800 μm, or at least about 850 μm, or at or least about 900 μm, or atleast about 1000 μm.

The screen sizes noted immediately above are applicable to the towermill embodiments described above.

As noted above, the grinding is performed in the presence of a grindingmedium. In an embodiment, the grinding medium is a coarse mediacomprising particles having an average diameter in the range of fromabout 1 mm to about 6 mm, for example about 2 mm, or about 3 mm, orabout 4 mm, or about 5 mm.

In another embodiment, the grinding media has a specific gravity of atleast about 2.5, for example, at least about 3, or at least about 3.5,or at least about 4.0, or at least 20 about 4.5, or least about 5.0, orat least about 5.5, or at least about 6.0.

As described above, the grinding medium (or media) may be in an amountup to about 70% by volume of the charge. The grinding media may bepresent in amount of at least about 10% by volume of the charge, forexample, at least about 20% by volume of the charge, or at least about30% by volume of the charge, or at least about 40% by volume of thecharge, or at least about 50% by volume of the charge, or at least about60% by volume of the charge.

In one embodiment, the grinding medium is present in amount of about 50%by volume of the charge. By ‘charge’ is meant the composition which isthe feed fed to the grinder vessel. The charge includes water, grindingmedia, the fibrous substrate comprising cellulose and any other optionaladditives (other than as described herein).

The use of a relatively coarse and/or dense media has the advantage ofimproved (i.e., faster) sediment rates and reduced media carry overthrough the quiescent zone and/or classifier and/or screen(s).

A further advantage in using relatively coarse screens is that arelatively coarse or dense grinding media can be used in themicrofibrillating step. In addition, the use of relatively coarsescreens (i.e., having a nominal aperture of least about 250 um) allows arelatively high solids product to be processed and removed from thegrinder, which allows a relatively high solids feed (comprising fibroussubstrate comprising cellulose and inorganic particulate material) to beprocessed in an economically viable process. As discussed below, it hasbeen found that a feed having a high initial solids content is desirablein terms of energy sufficiency. Further, it has also been found thatproduct produced (at a given energy) at lower solids has a coarserparticle size distribution.

As discussed in the ‘Background’ section above, the present inventionseeks to address the problem of preparing microfibrillated celluloseeconomically on an industrial scale.

Thus, in accordance with one embodiment, the fibrous substratecomprising cellulose is present in the aqueous environment at an initialsolids content of at least about 1 wt %. The fibrous substratecomprising cellulose may be present in the aqueous environment at aninitial solids content of at least about 2 wt %, for example at leastabout 3 wt %, or at least about at least 4 wt %. Typically the initialsolids content will be no more than about 10 wt %.

In another embodiment, the grinding is performed in a cascade ofgrinding vessels, one or more of which may comprise one or more grindingzones. For example, the fibrous substrate comprising cellulose may beground in a cascade of two or more grinding vessels, for example, acascade of three or more grinding vessels, or a cascade of four or moregrinding vessels, or a cascade of five or more grinding vessels, or acascade of six or more grinding vessels, or a cascade of seven or moregrinding vessels, or a cascade of eight or more grinding vessels, or acascade of nine or more grinding vessels in series, or a cascadecomprising up to ten grinding vessels. The cascade of grinding vesselsmay be operatively inked in series or parallel or a combination ofseries and parallel. The output from and/or the input to one or more ofthe grinding vessels in the cascade may be subjected to one or morescreening steps and/or one or more classification steps.

The total energy expended in a microfibrillation process may beapportioned equally across each of the grinding vessels in the cascade.Alternatively, the energy input may vary between some or all of thegrinding vessels in the cascade.

A person skilled in the art will understand that the energy expended pervessel may vary between vessels in the cascade depending on the amountof fibrous substrate being microfibrillated in each vessel, andoptionally the speed of grind in each vessel, the duration of grind ineach vessel and the type of grinding media in each vessel. The grindingconditions may be varied in each vessel in the cascade in order tocontrol the particle size distribution of the microfibrillatedcellulose.

In an embodiment the grinding is performed in a closed circuit. Inanother embodiment, the grinding is performed in an open circuit.

As the suspension of material to be ground may be of a relatively highviscosity, a suitable dispersing agent may preferably be added to thesuspension prior to grinding. The dispersing agent may be, for example,a water soluble condensed phosphate, polysilicic acid or a salt thereof,or a polyelectrolyte, for example a water soluble salt of a poly(acrylicacid) or of a poly(methacrylic acid) having a number average molecularweight not greater than 80,000. The amount of the dispersing agent usedwould generally be in the range of from 0.1 to 2.0% by weight, based onthe weight of the dry inorganic particulate solid material. Thesuspension may suitably be ground at a temperature in the range of from4° C. to 100° C.

Other additives which may be included during the microfibrillation stepinclude: carboxymethyl cellulose, amphoteric carboxymethyl cellulose,oxidising agents, 2,2,6,6-Tetramethylpiperidine-1-oxyl (TEMPO), TEMPOderivatives, and wood degrading enzymes.

The pH of the suspension of material to be ground may be about 7 orgreater than about 7 (i.e., basic), for example, the pH of thesuspension may be about 8, or about 9, or about 10, or about 11. The pHof the suspension of material to be ground may be less than about 7(i.e., acidic), for example, the pH of the suspension may be about 6, orabout 5, or about 4, or about 3. The pH of the suspension of material tobe ground may be adjusted by addition of an appropriate amount of acidor base. Suitable bases included alkali metal hydroxides, such as, forexample NaOH. other suitable bases are sodium carbonate and ammonia.Suitable acids included inorganic acids, such as hydrochloric andsulphuric acid, or organic acids. An exemplary acid is orthophosphoricacid.

The total energy input in a typical grinding process to obtain thedesired aqueous suspension composition may typically be between about100 and 1500 kWht⁻¹ based on the total dry weight of the inorganicparticulate filler. The total energy input may be less than about 1000kWht⁻¹, for example, less than about 800 kWht⁻¹, less than about 600kWht⁻¹, less than about 500 kWht⁻¹, less than about 400 kWht⁻¹, lessthan about 300 kWht⁻¹, or less than about 200 kWht⁻¹. As such, thepresent inventors have surprisingly found that a cellulose pulp can bemicrofibrillated at relatively low energy input when it is co-ground inthe presence of an inorganic particulate material. As will be apparent,the total energy input per tonne of dry fibre in the fibrous substratecomprising cellulose will be less than about 10,000 kWht⁻¹, for example,less than about 9000 kWht⁻¹, or less than about 8000 kWht⁻¹, or lessthan about 7000 kWht⁻¹, or less than about 6000 kWht⁻¹, or less thanabout 5000 kWht⁻¹. for example less than about 4000 kWht⁻¹, less thanabout 3000 kWht⁻¹, less than about 2000 kWht⁻¹, less than about 1500kWht⁻¹, less than about 1200 kWht⁻¹, less than about 1000 kWht⁻¹, orless than about 800 kWht⁻¹. The total energy input varies depending onthe amount of dry fibre in the fibrous substrate being microfibrillated,and optionally the speed of grind and the duration of grind.

With regard to the present invention, it has been found thatultrasonication of the aqueous suspension comprising microfibrillatedcellulose of the present invention (collectively referred to as the“aqueous suspension”) enhances physical properties of the material. Forexample, ultrasonication of an aqueous suspension comprisingmicrofibrillated cellulose surprisingly and unexpectedly results inenhanced viscosity and/or tensile strength of the material, asdemonstrated in the Examples section of this specification. Theenhancement of the physical properties of the material of the presentinvention and the degree of enhancement is dependent upon the operatingparameters used. In view of the teachings of this specification, one ofordinary skill in the art will be able to discern the parametersappropriate to achieve a desired result without undue experimentation.

In one aspect, the ultrasonication of the aqueous suspension of thepresent invention comprises producing an sonicated suspension comprisingmicrofibrillated cellulose with enhanced viscosity and/or tensilestrength properties, the method comprising a step of microfibrillating afibrous substrate comprising cellulose in an aqueous environment toproduce an aqueous suspension comprising microfibrillated cellulose, andfurther comprising subjecting the aqueous suspension comprisingmicrofibrillated cellulose to sonication to produce an aqueoussuspension comprising microfibrillated cellulose with enhanced viscosityand tensile strength properties.

In one embodiment, a grinding media, as discussed above, may also beused to produce the aqueous suspension comprising microfibrillatedcellulose with enhanced viscosity and tensile strength properties.

Ultrasonication of the aqueous suspension comprising microfibrillatedcellulose may be conducted with an ultrasonic probe or ultrasonic waterbath, an ultrasonic homogenizer, an ultrasonic foil or an ultrasonichorn. The use of such devices is known to one of ordinary skill in theart.

In an embodiment of the present invention, the methods of the presentinvention may further comprise one or more of high shear mixing,homogenisation or refining either before or after the sonication step,all of which are known by one of ordinary skill in the art and may beincorporated into the methods of the present invention without undueexperimentation in view of the teachings of this specification.

In an embodiment, ultrasonication is advantageously used to re-dispersepreviously dewatered, dried or partially dried compositions ofmicrofibrillated cellulose. The dried or partially dried compositions ofmicrofibrillated may be pelletized after dewatering and drying. Suchdried or partially dried and optionally pelletized compositions ofmicrofibrillated cellulose are re-suspended with the aid ofultrasonication devices of the types described in this specification.

In an embodiment ultrasonication is used as a post-treatment step onslurries of microfibrillated cellulose to improve one or more physicalproperty of such slurries, for example, increased tensile strength andenhanced viscosity.

In an embodiment of the present invention, the tensile strength of theaqueous suspension comprising microfibrillated cellulose with enhancedviscosity and tensile strength properties is increased by at least 5%,at least 10%, at least 20%, at least 50%, at least 100% or at least 200%over the aqueous suspension comprising microfibrillated cellulose notsubject to sonication.

In an embodiment of the present invention, the viscosity of the aqueoussuspension comprising microfibrillated cellulose with enhanced viscosityand tensile strength properties is increased by at least 5%, at least by10% or at least by 20%, by at least 50%, by at least 100% over theaqueous suspension comprising microfibrillated cellulose and inorganicparticulate material not subject to sonication.

In an embodiment of the present invention, the aqueous suspensioncomprising microfibrillated cellulose is subject to sonication for atleast 30 seconds, at least 1 minute, at least 2 minutes, at least 5minutes, at least 10 minutes and at least 20 minutes or longer. Thelength of time may be determined by one of ordinary skill in the artbased on the teachings of this specification.

In an embodiment of the present invention, the aqueous suspensioncomprising microfibrillated cellulose is subject to sonication at anenergy compensation rate of up to 1000 kwh per tonne of dried fibrils,up to 2000 kwh per tonne, 2500 kwh per tonne of dried fibrils, up to5000 kwh per tonne of dried fibrils and up to 10000 kwh per tonne ofdried fibrils. As set forth in the Examples of this application,sonication was found to be more effective for re-dispersing andde-agglomerating microfibrillated cellulose or compositions ofmicrofibrillated cellulose and inorganic particulate material that hadbeen dewatered, dried and pelletized. In other embodiments,re-dispersion of slurries of slurries of microfibrillated cellulose orcompositions of microfibrillated cellulose and inorganic particulatematerial through sonication yielded improvements in product quality atenergy inputs between 1000 and 2000 kWh/t.

In an embodiment, sonication of mineral free microfibrillated cellulose(e.g., birch) produced using the a pilot scale stirred media detritor(Supermill) yielded products with comparable specifications tomicrofibrillated cellulose made by grinding processes in, for example aSupermill, followed by a homogenization step when sonicated at about1500 kWh/t.

In certain embodiments, the aqueous suspension comprisingmicrofibrillated cellulose may be sonicated by running the sonicator incontinuous mode or in pulse mode or a combination of both. That is,where alternating long pulses and short pulses are performed as desiredpatterns or at random.

In preferred embodiments, the aqueous suspension comprisingmicrofibrillated cellulose may be formed into a semi-dry product priorto sonication. A belt pressed cake is one example of a semi-driedproduct suitable for use in the present invention. In certainembodiments, the belt press cake may be further subjected to treatmentin an air swept dryer and mill, such as an Atritor dryer. Oftenconverting the product to a semi-dry product is done, for example, forease of handling and/or transport. In the event of using a semi-driedproduct as a starting material, sonication not only provides enhancedphysical properties to the material but also aids in disbursement of thematerial into solution in a process referred to as rewetting.

The sonication of the aqueous suspension comprising microfibrillatedcellulose is not limited to any particular or specific sonicationparameters as a change on one parameter may compensate for a change inanother parameter, within physical and practical limits of the equipmentand material being sonicated. For example, lengthening sonication timemay compensate at least partly for using a reduced amplitude.

In preferred embodiments, the sonication is performed at an amplitude ofup to 60%, up to 80%, up to 100% and up to 200% or more, to the physicallimitations of the sonicator used. Said upper physical limits ofamplitude of a particular device used are known to one of ordinary skillin the art.

The fibrous substrate comprising cellulose may be in the form of a pulp,for example, a chemical pulp, or a chemithermomechanical pulp, or amechanical pulp, or a recycled pulp, or a paper broke pulp, or apapermill waste stream, or waste from a papermill, or combinationsthereof.

The grinding vessel may be a tower mill or a stirred media detritor.

In an embodiment, the aqueous suspension comprising microfibrillatedcellulose with enhanced viscosity and tensile strength propertiesobtained by the method of the present invention is suitable for use in amethod of making paper or coating paper and is suitable for other use inother processes and materials where microfibrillated cellulose istypically used, examples of which are detailed below in the sectionentitled “Other Uses.”

Other Uses

The compositions of the present invention of microfibrillated celluloseor microfibrillated cellulose and inorganic particulate material withenhanced viscosity and/or tensile strength properties andmicrofibrillated cellulose with enhanced viscosity and/or tensilestrength may be used in numerous applications. For example, thecompositions of the present can be used for paper, paper board and papercoatings, as discussed above; paints and other coatings as, for examplea rheology modifier; inks; and as a thickener, stabilizer, andhomogenizing agent for use in, for example, foods and food additives,pharmaceuticals, cosmetics, sunscreens, adhesives, sealants, consumerchemicals such as but not limited to detergents, fabric softeners andother household products; oilfield chemicals such as corrosion and scaleinhibitors as well as an ingredient in petroleum by-products; andcomposites, such as wallboard and ceiling tiles. The compositions of thepresent invention are also suitable for use in cement board, gypsumboard/plasterboard; insulation core of structural insulated panels andfiber boards; fiberboards of all descriptions (including orientedparticle board); cements and concretes; sound proofing; textured andmasonry paints; antimicrobial and fire retardant wall boards; sealantsand adhesives and caulks; insulation; partial or complete asbestosreplacement; and foams, wherein the composition of the present inventioncan, for example, provide strength, bulk and texture.

EXAMPLES

Embodiments of the present invention will now be described by way ofillustration only, with reference to the following examples.

The following procedure we use to characterise the particle sizedistributions of mixtures of minerals (GCC or kaolin) andmicrofibrillated cellulose pulp fibres.

Calcium Carbonate

A sample of co-ground slurry sufficient to give 3 g dry material isweighed into a beaker, diluted to 60 g with deionised water, and mixedwith 5 cm³ of a solution of sodium polyacrylate of 1.5 w/v % active.Further deionised water is added with stirring to a final slurry weightof 80 g.

Kaolin

A sample of co-ground slurry sufficient to give 5 g dry material isweighed into a beaker, diluted to 60 g with deionised water, and mixedwith 5 cm³ of a solution of 1.0 wt % sodium carbonate and 0.5 wt %sodium hexametaphosphate. Further deionized water is added with stirringto a final slurry weight of 80 g.

The slurry is then added in 1 cm³ aliquots to water in the samplepreparation unit attached to the Mastersizer S until the optimum levelof obscuration is displayed (normally 10-15%). The light scatteringanalysis procedure is then carried out. The instrument range selectedwas 300RF: 0.05-900, and the beam length set to 2.4 mm.

For co-ground samples containing calcium carbonate and fibre therefractive index for calcium carbonate (1.596) was used. For co-groundsamples of kaolin and fibre the RI for kaolin (1.5295) was used.

The particle size distribution was calculated from Mie theory and gavethe output as a differential volume based distribution. The presence oftwo distinct peaks was interpreted as arising from the mineral (finerpeak) and fibre (coarser peak).

The finer mineral peak was fitted to the measured data points andsubtracted mathematically from the distribution to leave the fibre peak,which was converted to a cumulative distribution. Similarly, the fibrepeak was subtracted mathematically from the original distribution toleave the mineral peak, which was also converted to a cumulativedistribution. Both these cumulative curves were then used to calculatethe mean particle size (d₅₀) and the steepness of the distribution(d₃₀/d₇₀×100). The differential curve was used to find the modalparticle size for both the mineral and fibre fractions.

Example 1

400 cm³ water and 750 g of marble flour (10 wt % <2 μm particle size, bySedigraph) were introduced into a grinding vessel and 1.5 kg of ceramicgrinding media (Carbolate® 16/20, available from CARBO Ceramics Inc.)added. The mixture was stirred at 950 rpm for 60 minutes. The media wasseparated from the slurry and a small sample was removed to check theparticle size (using a Micromeritics Sedigraph®) which was 57 wt % <2μm.

The same grinder was used for each of the Examples. This grinder is avertical mill comprising a cylindrical grinding vessel having aninternal diameter of 14.5 cm and a vertical impeller shaft having acircular cross section and a diameter 1.8 cm. The shaft is equipped with4 impellers positioned in an X design. The impellers have a circularcross section and a diameter 1.8 cm. The impellers are 6.5 cm longmeasured from the center of the vertical shaft to the impeller tip.

Example 2

400 cm³ water and 750 g of marble flour (11-15 wt % <2 μm particle size,by Sedigraph) were introduced into a grinding vessel and 1.5 kg ofceramic grinding media (Carbolite® 16/20, available from CARBO CeramicsInc.) added. The mixture was stirred at 950 rpm for 30 minutes. A smallsample was removed and the particle size of the product was measured(using a Micromeritics Sedigraph®) at 57 wt % <2 μm. An aliquot ofbleached softwood pulp beaten in a Valley beater to a Canadian StandardFreeness (CSF) of 520 cm³ was filtered through a screen in order toobtain a wet sheet at 20 wt % solids containing 37.5 dry g fibre. Thissheet was added to the grinder and milling continued at 950 rpm for afurther 30 minutes. 200 cm³ of water was added during the grinding. Themedia was separated from the slurry, and the fibres greater than 38 μmremoved using a BSS sieve having a mesh number of 400. The particle sizeof the filler composition was measured (using a MicromeriticsSedigraph®) and gave a result of 48 wt % <2 μm.

Example 3

The procedure described in Example 2 was repeated, this time continuingthe second milling stage for 60 minutes. 200 cm³ of water was addedduring the grinding. The particle size distribution of the product wasmeasured and gave a value of 42 wt % <2 μm.

Example 4

The procedure described in Example 2 was repeated, this time continuingthe second milling stage for 120 minutes. 650 cm³ of water was addedduring the grinding. The particle size distribution of the product wasmeasured and gave a value of 40 wt % <2 μm.

Example 5

The procedure described in Example 2 was repeated, this time continuingthe second milling stage for 260 minutes. 1270 cm³ of water was addedduring the grinding. The particle size distribution of the product wasmeasured and gave a value of 40 wt % <2 μm.

Example 6

The procedure described in Example 2 was repeated, this time continuingthe second milling stage for 380 minutes. 1380 cm³ of water was addedduring the grinding. The particle size distribution of the product wasmeasured and gave a value of 57 wt % <2 μm.

Example 7—Evaluation of the Products as Fillers in Paper

Some of the products prepared according to the above examples weretested as fillers in paper handsheets. A batch of bleached chemicalsoftwood pulp was used which was beaten in a Valley beater to give a CSFof 520 cm³. After disintegration and dilution to 2% thick stock, thefibre was diluted to 0.3 wt % consistency for sheet making.

Filler slurry was added together with retention aid (Ciba Percol 292,0.02 wt % on furnish). Handsheets were made to a basis weight of 80 gm⁻²using a British handsheet mold according to standard methods, e.g.,TAPPI T205 or SCAN C 26:76 (M 5:76).

The retention values of the fillers are listed below in Table 1, andshow that the co-ground fillers have superior retention to the controlfiller.

TABLE 1 First pass retention values Ex. 1 control Ex. 2 co-ground Ex. 3co-ground 51% 63% 63%

Two separate sheet making studies were performed and the results aregiven in Tables 2 and 3 below. Paper properties are interpolated at 30wto/o loading and were measured according to standard test methods,e.g., TAPPI T220 or SCAN C28:76 (M 8:76).

-   -   Burst strength: Messemer Buchnel burst tester according to SCAN        P 24.    -   Tensile strength: Testometrics tensile tester according to SCAN        P 16.    -   Bendtsen porosity: Measured using a Bendtsen Model porosity        tester in accordance with SCAN P21, SCAN P60, BS 4420 and Tappi        UM 535.    -   Bulk: This is the reciprocal of the apparent density as measured        according to SCAN P7.    -   ISO Brightness: The ISO brightness of handsheets was measured by        means of an Elrepho Datacolour 3300 brightness meter fitted with        a No. 8 filter (457 nm wavelength), according to ISO 2470: 1999        E.    -   Opacity: The opacity of a sample of paper is measured by means        of an Elrepho Datacolor 3300 spectra-photometer using a        wavelength appropriate to opacity measurement. The standard test        method is ISO 2471. First, a measurement of the percentage of        the incident light reflected is made with a stack of at least        ten sheets of paper over a black cavity (Rinfinity). The stack        of sheets is then replaced with a single sheet of paper, and a        second measurement of the percentage reflectance of the single        sheet on the black cover is made (R). The percentage opacity is        then calculated from the formula: Percentage        opacity=100×R/Rinfinity.

TABLE 2 Burst Burst Tensile Tensile Bendtsen Index strength indexstrength porosity Bulk Brightness % Opacity Filler Nm g⁻¹ % unfilled Nmg⁻¹ % unfilled cm³ min⁻¹ cm³ g⁻¹ F8 F10 Unfilled 54 100 59.5 100 7901.64 84.9 74.0 Ex. 1 11 21.0 14 26.0 1900 1.53 90.6 89.0 Ex. 2 18 31.024 40.5 1490 1.51 89.3 88.1 Ex. 3 15 28.0 23 39.0 1490 1.49 89.0 88.1

TABLE 3 Burst Burst Tensile Tensile Bendtsen Index strength indexstrength porosity Bulk Brightness % Opacity Filler Nm g⁻¹ % unfilled Nmg⁻¹ % unfilled cm³ min⁻¹ cm³ g⁻¹ F8 F10 Unfilled 55.5 100 63 100 6501.59 85.5 73.7 Ex. 1 9.5 17.5 15 25.0 2250 1.55 90.7 88.9 Ex. 4 15 26.022.5 35.0 700 1.46 90.5 88.5 Ex. 5 16 30.0 23 35.0 500 1.44 90.1 88.9Ex. 6 16 30.0 24 39.0 400 1.45 89.7 89.4

Example 8

4 dry kg of a kaolin filler, Intramax® 57, was dispersed in 6000 cm³water using a high energy mixer. The pH was 4.8. This was used as astock suspension for further experiments. The particle size distributionwas measured (using a Micromeritics Sedigraph®) and gave values of 57 wt% <2 μm, and 38 wt % <1 μm.

Example 9

2 kg of the above stock suspension of kaolin was processed for 5 passesthrough a Manton Gaulin (APV) homogeniser at a pressure of 500 bar. Theresulting product was used as a control in further papermaking tests.The particle size distribution was measured (using a MicromeriticsSedigraph®) and gave values of 62 wt % <2 μm, and 43 wt % <1 μm.

Example 10

A further 2 kg of the stock kaolin suspension was placed on a highenergy mixer. A suspension of bleached softwood pulp was beaten on aValley beater to a CSF of 520 cm³ and this was filtered on a standardconsistency tester to give a wet sheet at 15% dry solids. 133.5 g ofthis wet pulp was added to the kaolin suspension and stirred until thefibres were well mixed with the kaolin, to give a level of 2.5 wt % drypulp on dry kaolin. 440 cm³ of water was also added to improveflowability. This suspension at 33 wt % solids was then passed throughthe Gaulin homogeniser under the same conditions as Example 9. Theparticle size distribution of the product was measured (using aMicromeritics Sedigraph®) and gave values of 62 wt % <2 μm, and 45 wt %<1 μm.

Example 11

The procedure described in Example 10 was repeated, this time adding 267g wet pulp to 2 kg stock kaolin suspension, to give a level of 5 wt %dry pulp on dry kaolin. The suspension was also diluted to about 30 wt %solids with 440 cm³ water, and the suspension processed through thehomogeniser using the same conditions as Examples 9 and 10. The particlesize distribution was measured (using a Micromeritics Sedigraph®) andgave values of 58.5 wt % <2 μm, and 42 wt % <1 μm.

Example 12—Evaluation of the Products as Fillers in Paper

The products prepared according to the above examples were tested asfillers in paper handsheets. A batch of bleached chemical softwood pulpwas used which was beaten in a Valley beater to give a CSF of 520 cm³.After disintegration and dilution to 2% thick stock, the fibre wasfurther diluted to 0.3 wt % consistency for sheet making. Filler slurrywas added together with retention aid (Ciba Percol 292, 0.02 wt % onfurnish). Handsheets were made to a basis weight of 80 gm⁻² using aBritish handsheet mold.

The retention values of the fillers are listed below in Table 4, andshow that the co-processed fillers have superior retention to thecontrol filler.

TABLE 4 First pass retention values Ex. 9 control Ex. 10 co-processedEx. 11 co-processed 54% 66% 71%

A sheet making study was performed and the results are given in Table 5below. Paper properties are interpolated at 30 wt % loading.

TABLE 5 Tensile Tensile Bendtsen PPS index strength porosity BulkRoughness Brightness % Opacity Filler Nmg⁻¹ % unfilled cm³ min⁻¹ cm³ g⁻¹1000 kPa F8 F10 Unfilled 64 100 785 1.58 10.0 85.5 72.8 Ex. 9 20 31.0755 1.48 8.4 82.2 91.9 Ex. 10 24 39.0 610 1.47 8.6 82.2 91.9 Ex. 11 3046.0 780 1.50 9.0 82.2 91.9

Example 13

400 g of unrefined bleached softwood kraft pulp (Botnia Pine RM90) wassoaked in 20 litres of water for 6 hours, then slushed in a mechanicalmixer. The stock so obtained was then poured into a laboratory Valleybeater and refined under load for 28 mins to obtain a sample of refinedpulps beaten to 525 cm³ Canadian standard Freeness (CSF). A secondsample was prepared by slushing but not refining at all. The freenessresults and refining times are given in Table 6 below:

TABLE 6 Refining Conditions Refining time, mins CSF, cm² Pulp Sample A 0705 Sample B 28 525

Each of these pulps were then dewatered using a consistency tester(Testing Machines Inc.) to obtain a pad of wet pulp at between 13 and 18wt % solids. This was then used in co-grinding experiments as detailedbelow:

630 g of a slurry of ground marble having a particle size (measured bySedigraph) of 60% <2 μm e.s.d was weighed into a grinding vessel. Thedry weight was 233 g. Wet pulp from the dewatering stage described abovewas added to give 11.6 g (dry weight) of pulp. The pulp was thoroughlymixed with the mineral slurry and then 1485 g Carbolite® 16/20 media andrequired water added to give a media volume, concentration (MVC) of 50%and a slurry solids content of 35 wt %. The samples were ground at 1000RPM until an energy input of 2500 and 5000 kWh/t (expressed on dryfibre) had been imparted to the samples. The vessel was then removedfrom the grinder and the media separated using a screen having anaperture size of 600 μm.

Products made from Pulp sample A (unrefined) and B (refined to 525 cm³)were compared using the Filter Paper Burst Increase (FPBI) test (asdescribed below). The results are summarised in Table 7.

TABLE 7 Filter paper burst increase Pulp/energy Wt % fibre Fibre usedduring on product Fibre steepness(d₃₀/ FPBI Filler co-grinding by ashd₅₀ μm d₇₀ × 100) % Control Water only — — — 10.3 1 Pulp A 2500 4.3 98.628.7 25.2 kWh/t 2 Pulp A 5000 4.9 32.9 37.7 21.4 kWh/t 3 Pulp B 2500 5.080.0 31.7 20.0 kWh/t 4 Pulp B 5000 5.0 26.5 40.2 22.9 kWh/t

Filter Paper Burst Test

This test was developed to predict the fibre reinforcing ability of aco-ground slurries containing MFC prepared in accordance with Example 13above.

15 cm diameter filter papers (No. 597, Schleicher & Schuell) were used.Sheets were selected by weight to be within 0.02 g of each other. Atypical dry weight of a single sheet was 1.4 g.

A suspension of co-ground mineral and pulp was prepared as describedabove and diluted with water to a solids of 0.25%. A single filter paperselected above was wetted with water and placed on the wire of astandard consistency testing apparatus (TMI Testing Machines Inc.,Ronkonkoma, N.Y.). Aliquots of the suspension from 150 cm³, 200 cm³, 250cm³ and 300 cm³ were carefully filtered using applied vacuum through thefilter paper and the filtrates, if cloudy, re-passed through the mat toensure good retention of the active components. The filter paper and itsretained solids was then dried at 50% RH and 23° C. supported on steeldrying discs and separated by plastic drying rings (Testing MachinesInc.).

The dried papers were tested for burst strength using a Messemer Buchelautomatic burst tester. 5 measurements were obtained on each sheet andaveraged. The sheets were then dried at 100° C. for 1 hour, placed in asealed tared container, and weighed to 3 dp. A plot was constructed ofsheet weight against burst pressure, from which the burst pressure at aweight of 2.0 g was interpolated {a kPa). The mean burst pressure of thefilter paper itself {b kPa) was also measured on 3 selected sheets,conditioned under the same temperature and humidity. The increase inburst pressure was then calculated by the following equation:Filter paper burst increase (FPBI)=(a−b)/b×100.

As a control, water only was passed through the filter paper disc. Thisalso had a positive effect on burst, but significantly less than whenMFC was present {see Table 7).

The samples produced above were additionally characterised in terms oftheir particle size using the Malvern Mastersizer {Malvern Instruments,UK). The results are recorded in terms of the mean (d₅₀) sizes of thepulp fractions. The particle size steepness of the fibre fraction wasalso recorded. These data are also listed in Table 7.

Samples made from Pulps A and B were further compared in a handsheetstudy. The host pulp for these fillers was prepared from the same BotniaRM90 batch beaten to a CSF of 520 cm³, similar to Sample B. Retentionaid was Percol 292 (Ciba) added at 0.06 wt % on total furnish solids.Handsheets were prepared at 80 gm⁻² and tested for burst and tensilestrength, bulk, Bendtsen porosity, reflectance at 457 nm (ISObrightness), and opacity. 3 loadings were obtained and results areinterpolated to a loading level of 30 wt % (see Table 8). Fillerdesignations refer to Table 7.

The results in Table 8 show that the co-ground fillers give increasedstrength, reduced porosity and increased opacity without detriment tothe brightness, all desirable properties. The increase in strength issufficient to allow the loading of filler to be increased from 25 wt %using standard GCC filler to 33 wt % with co-ground filler.

TABLE 8 Handsheet results Burst Tensile Bendsten index index porosityBulk Brightness % Opacity Filler Nmg⁻¹ Nmg⁻¹ cm³ min⁻¹ cm³ g⁻¹ F8 F10Unfilled 65.4 64.9 481 1.51 86.4 72.5 Control 13.5 19.5 1500 1.525 90.888.2 60-2 μm GCC 1 19.5 25.5 510 1.43 91.0 89.1 2 19 25 420 1.40 90.989.1 3 18.5 28.5 340 1.41 91.0 89.4 4 17.5 25.5 390 1.41 91.0 89.9

Example 14

400 g of unrefined bleached softwood kraft pulp (Botnia Pine RM90) wassoaked in 20 litres of water for 6 hours, then slushed in a mechanicalmixer. The stock so obtained was then poured into a laboratory Valleybeater and refined under load for 28 mins to obtain a sample of refinedpulp beaten to 525 cm³ Canadian Standard Freeness (CSF). The pulp wasthen dewatered using a consistency tester (Testing Machines Inc.) toobtain a pad of wet pulp at 19.1 wt % solids. This was then used inco-grinding experiments as detailed below:

651 g of a slurry of Carbital 60HS™ (solids 77.9 wt %) was weighed intoa grinding pot. 66.5 g of wet pulp was then added and mixed with thecarbonate. 1485 g of Carbolite® 16/20 grinding media was then addedfollowed by 147 g water to give a media volume concentration of 50%. Themixture was ground together at 1000 rpm until an energy input of 10,000kWh/t (expressed on fibre) had been expended. The product was separatedfrom the media using a 600 μm BSS screen. The solids content of theresulting slurry was 59.4 wt % and a Brookfield viscosity (100 rpm) of10,000 mPa·s. The fibre content of the product was analysed by ashing at450° C. and the size of the mineral and pulp fractions measured using aMalvern Mastersizer.

Example 15

352 g of a slurry of Carbital 60HS™ (solids 77.9 wt %) was weighed intoa grinding pot. 71.8 g of wet pulp was then added and mixed with thecarbonate. 1485 g of Carbolite 16/20 grinding media was then addedfollowed by 296 g water to give a media volume concentration of 50%. Themixture was ground together at 1000 rpm until an energy input of 10,000kWh/t (expressed on fibre) had been expended. The product was separatedfrom the media using a 600 μm BSS screen. The solids content of theresulting slurry was 41.9 wt % and a Brookfield 100 rpm viscosity of5000 mPa·s. The fibre content of the product was analysed by ashing at450° C. and the size of the mineral and pulp fractions measured using aMalvern Mastersizer.

Example 16

287 g of a slurry of Carbital 60HS™ (solids 77.9 wt %) was weighed intoa grinding pot. 87.9 g of wet pulp was then added and mixed with thecarbonate. 1485 g of Carbolite 16/20 grinding media was then addedfollowed by 311 g water to give a media volume concentration of 50%. Themixture was ground together at 1000 rpm until an energy input of 10,000kWh/t (expressed on fibre) had been expended. The product was separatedfrom the media using a 600 μm BSS screen. The solids content of theresulting slurry was 36.0 wt % and a Brookfield 100 rpm viscosity of7000 mPa·s. The fibre content of the product was analysed by ashing at450° C. and the size of the mineral and pulp fractions measured using aMalvern Mastersizer.

TABLE 9 Physical properties of pigments Mean Mean GCC GCC steepnessfibre size Wt % fibre Filler size, d₅₀, μm (d₃₀/d₇₀ × 100) d₅₀, μm inproduct Carbital 60HS 1.49 28.1 — 0 Carbital 90HS 0.86 35.6 — 0Carbopaque 90 0.78 40.6 — 0 Ex 14 0.95 35.0 13.6 3.3 Ex 15 0.69 40.210.1 5.6 Ex 16 0.68 42.5 10.9 8.1

Table 9 shows that, in addition to grinding the fibre to a fine particlesize, the fineness and psd steepness of the GCC was also increased tomatch those of the finer control pigments, Carbital 90™ and Carbopaque90™.

The references and co-ground pigments described above were made intocoating colours and a coating study carried out according to thefollowing examples.

Example 17 (Control)

129 g of Carbital 60HS(=100 g dry) were weighed into a beaker, mixedusing a laboratory stirrer, and 14 g of a 50% suspension ofstyrene-butadiene-acrylonitrile latex (DL920, Dow Chemical) added togive a binder dose of 7 parts latex per hundred of calcium carbonate(pph). 0.3 dry g of carboxymethyl cellulose (Finnfix 10, CP Kelco) wasthen added as a 12% solution, followed by 0.5 g of a solution of opticalbrightening agent (Blankophor P, Kemira). The pH was adjusted to 8.7using NaOH. A second colour was prepared using an increased latex doseof 9 pph.

Example 18 (Control)

129.7 g of Carbital 90HS(=100 g dry) were weighed into a beaker, mixedusing a laboratory stirrer, and 16 g of a 50% suspension ofstyrene-butadiene-acrylonitrile latex (DL920, Dow Chemical) added togive a binder dose of 8 parts latex per hundred of calcium carbonate(pph). 0.3 dry g of carboxymethyl cellulose (FinnflX 10, CP Kelco) wasthen added as a 12% solution, followed by 0.5 g of a solution of opticalbrightening agent (Blankophor P, Kemira). The pH was adjusted to 8.9using NaOH. A second colour was prepared using an increased latex doseof 10 pph.

Example 19 (Control)

139 g of Carbopaque 90 (=100 g dry) were weighed into a beaker, mixedusing a laboratory stirrer, and 16 g of a 50% suspension ofstyrene-butadiene-acrylonitrile latex (DL920, Dow Chemical) added togive a binder dose of 8 parts latex per hundred of calcium carbonate(pph). 0.3 dry g of carboxymethyl cellulose (Finnfix 10, CP Kelco) wasthen added as a 12% solution, followed by 0.5 g of a solution of opticalbrightening agent (Blankophor P, Kemira). The pH was adjusted to 8.6using NaOH. A second colour was prepared using an increased latex doseof 10 pph.

Example 20 (Control)

129.7 g of Carbital 90HS(=100 g dry) were weighed into a beaker, and 2.5g of a commercially available powdered cellulose of 1000 nm averageparticle size (manufacturer's value) intended for paper coating (ArbocelMF40, J. Rettenmaier & Sohne, Holzmuhle, Germany), was added with mixingusing a laboratory stirrer. When the powder had been fully dispersed, 15g of a 50% suspension of styrene-butadiene-acrylonitrile latex (DL920,Dow Chemical) was added to give a binder dose of 7.5 parts latex perhundred of calcium carbonate (pph). 0.3 dry g of carboxymethyl cellulose(FinnflX 10, CP Kelco) was then added as a 12% solution, followed by 0.5g of a solution of optical brightening agent (Blankophor P, Kemira). ThepH was adjusted to 8.6 using NaOH.

Example 21

173.4 g of the product prepared according to Ex 14 (=103 g dry) wereweighed into a beaker, mixed using a laboratory stirrer, and 14 g of a50% suspension of styrene-butadiene-acrylonitrile latex (DL920, DowChemical) added to give a binder dose of 7 parts latex per hundred ofdry calcium carbonate (pph). 0.3 dry g of carboxymethyl cellulose(FinnflX 10, CP Kelco) was then added as a 10% solution, followed by 0.5g of a solution of optical brightening agent (Blankophor P, Kemira). ThepH was adjusted to 8.8 using NaOH. A second colour was prepared using anincreased latex dose of 9 pph.

Example 22

250.6 g of the product prepared according to Ex 15 (=105 g dry) wereweighed into a beaker, mixed using a laboratory stirrer, and 14 g of a50% suspension of styrene-butadiene-acrylonitrile latex (DL920, DowChemical) added to give a binder dose of 7 parts latex per hundred ofdry calcium carbonate (pph). 0.3 dry g of carboxymethyl cellulose(Finnfix 10, CP Kelco) was then added as a 10% solution, followed by0.375 g of a solution of optical brightening agent (Blankophor P,Kemira). The pH was adjusted to 8.6 using NaOH. A second colour wasprepared using an increased latex dose of 9 pph.

The colours were coated onto a mechanical basepaper of substance 70 gm·2using a laboratory web coater (Dow coater) with blade metering. The coatweight was adjusted by diluting the colour until the highest coat weightwas obtained, subsequently increasing the blade load to reduce the coatweight. Paper samples were produced having coat weight values from about8 gm·2 to 12 gm⁻². The speed was about 10 m min⁻¹.

The coated paper samples were then cut into strips and conditioned for24 hours at 50% RH and 23° C. before testing for brightness using aDatacolor Elrepho 3300 spectrophotometer. Reflectance measurements weremade at 457 nm with and without the UV component in the incident lightbeam. The difference between the reflectance values with and without UVis recorded as the fluorescence. The smoothness of the coated papers wasmeasured by an air leak method using a Parker Print Surf instrument at apressure of 1000 kPa. Each of the values was plotted against the coatweight as measured by ash. The results were then interpolated to acommon coat weight of 10 gm⁻² and tabulated in Table 11.

TABLE 10 Coating colour properties Latex Solids Brookfield 100 rpm levelpph wt % viscosity, mPa · s Ex 17 7 50.0 52 9 49.2 52 Ex 18 8 50.0 62 1042.7 86 Ex 19 8 50.1 67 10 49.9 69 Ex 20 7.5 45.8 67 Ex 21 7 45.0 1008 944.9 928 Ex 22 7 38.2 1444 9 38.3 1280

TABLE 11 Paper properties at 10 gm⁻² PPS Latex Brightness + FluorescenceSmoothness level pph UV % % 1000 kPa μm Ex 17 7 79.3 2.2 7.5 9 79.5 2.37.6 Ex 18 8 79.5 2.4 7.8 10 79.2 2.4 7.7 Ex 19 8 80.6 2.3 7.2 10 80.52.2 7.2 Ex 20 7.5 80.4 3.1 7.6 Ex 21 7 83.0 4.9 6.7 9 82.4 5.0 6.8 Ex 227 83.9 5.2 6.9 9 83.7 5.2 6.9

The results in Table 11 show that the invention gives increasedbrightness, fluorescence and increased smoothness.

Example 23

630 g of a slurry of ground marble having a particle size (measured bySedigraph) of 60% <2 μm e.s.d was weighed into a grinding vessel. Thedry weight was 233 g. 54 g of wet Eucalyptus pulp beaten to a CSF of 525cm³ (see Table 12) were added, equivalent to 11.6 g dry weight. The pulpwas thoroughly mixed with the mineral slurry and then 1485 g Carbolite16/20 media and 16 cm³ water added. This equates to a media volumeconcentration (MVC) of 50% and a slurry solids content of 35 wt %. Thesamples were ground at 1000 RPM until an energy input of 2500 and 5000kWh/t (expressed on dry fibre) had been imparted to the samples. Thetemperature reached 55° C. The vessel was then removed from the grinderand the media separated using a screen having an aperture size of 600μm.

Example 24

The procedure described in Example 23 was repeated, this time using ableached kraft softwood pulp (Botnia Pine RM90) beaten to 520 cm³ CSF.

Example 25

The procedure described in Example 23 was repeated, this time using asample of disintegrated thermomechanical pulp having a CSF of 700 cm³.

Example 26

The procedure described in Example 23 was repeated, this time using asample of Acacia pulp beaten to a CSF of 520 cm³.

Example 27

The procedure described in Example 23 was repeated, this time using asample of hardwood (birch) pulp beaten to a CSF of 520 cm³.

The fibre reinforcing ability of co-ground slurries containing MFCprepared in accordance with Examples 23-27 above was determined usingthe filter paper burst test described above. Results are given in table12 below.

The samples produced above were additionally characterised in terms oftheir particle size using the Malvern Mastersizer (Malvern Instruments,UK). The results are recorded in terms of the mean (d₅₀) sizes of theGCC and pulp fractions. The particle size steepness of the fibrefraction was also recorded. These data are also listed in Table 12.

These results show that all the pulp types produce strength increaseswhen subjected to co-grinding with GCC.

TABLE 12 Evaluation of the products using the filter paper test wt %fibre on mineral GCC Fibre Fibre FPBI % Example Pulp by ash d₅₀ μm d₅₀μm steepness (d₃₀/d₇₀ × 100) Control Water only — — — — 10.3 23aEucalyptus 4.6 1.55 54.0 37.8 23.0 2500 kWh/t 23b Eucalyptus 4.7 1.321.5 40.0 22.2 5000 kWh/t 24a TMP 5.4 1.55 44.0 32.8 17.0 2500 kWh/t 24bTMP 6.0 1.4 18.5 38.1 26.4 5000 kWh/t 25a Pine 5.0 1.6 75.0 33.2 20.02500 kWh/t 25b Pine 5.3 1.4 29.0 37.3 21.3 5000 kWh/t 26a Acacia 5.3 1.554.5 39.3 16.0 2500 kWh/t 26b Acacia 6.3 1.3 23.0 40.1 21.8 5000 kWh/t27a Birch 5.0 1.55 56.5 36.0 21.0 2500 kWh/t 27b Birch 4.6 1.15 17.037.8 25.5 5000 kWh/t

Example 28

400 g of unrefined bleached softwood kraft pulp (Botnia Pine RM90) wassoaked in 20 litres of water for 6 hours, then slushed in a mechanicalmixer. The stock so obtained was then poured into a laboratory Valleybeater and refined under load for 28 mins to obtain a sample of refinedpulp beaten to 525 cm³ Canadian Standard Freeness (CSF).

The pulp was then dewatered using a consistency tester (Testing MachinesInc.) to obtain a pad of wet pulp at 19.1 wt % solids. This was thenused in grinding experiments as detailed below.

Example 29

584 g of a slurry of ground marble having a particle size (measured bySedigraph) of 60% <2 μm e.s.d was weighed into a grinding vessel. Thedry weight was 231 g. Wet pulp from the dewatering stage described above(Example 28) was added to give 11.6 g (dry weight) of pulp. The pulp wasthoroughly mixed with the mineral slurry and then 1485 g Carbolite 16/20media and required water added to give a media volume concentration(MVC) of 50% and a slurry solids content of 35 wt %. The sample wasground at 1000 RPM until an energy input of 2500 kWh/t and 5000 kWh/t(expressed on dry fibre) had been imparted to the samples. The vesselwas then removed from the grinder and the media separated using a screenhaving an aperture size of 600 μm. The fibre content of the product wasanalysed by ashing at 450° C. and the size of the mineral and pulpfractions measured using a Malvern Mastersizer (see Table 13).

Example 30

176 g of a slurry of ground marble having a particle size (measured bySedigraph) of 60% <2 μm e.s.d was weighed into a grinding vessel. Thedry weight was 65 g. Wet pulp from the dewatering stage described abovewas added to give 8.5 g (dry weight) of pulp. The pulp was thoroughlymixed with the mineral slurry and then 1485 g Carbolite 16/20 media andrequired water added to give a media volume concentration (MVC) of 50%and a slurry solids content of 12.5 wt %. The samples were ground at1000 RPM until an energy input of 3750 and 5000 kWh/t (expressed on dryfibre) had been imparted to the samples. The vessel was then removedfrom the grinder and the media separated using a screen having anaperture size of 600 μm. The fibre content of the product was analysedby ashing at 450° C. and the size of the mineral and pulp fractionsmeasured using a Malvern Mastersizer (see Table 13).

TABLE 13 GCC modal particle Fibre wt % fibre Filler size, μm d₅₀, μm inproduct Control 60-2 μm 2.72 — 0 GCC Ex 29 2500 kW 2.1  66.5 4.5 Ex 295000 kW 1.73 26   4.7 Ex 30 3750 kW 1.61 65   11.7 Ex 30 5000 kW 1.4142   11.7

Example 31

Handsheet Evaluation

Samples made in Examples 29 and 30 were compared in a handsheet study.The control filler was the same 60% <2 μm ground marble used in thegrinding experiments. The host pulp for these fillers was prepared fromthe same Botnia RM90 batch beaten to a CSF of 520 cm³. Retention aid wasPercol 292 (Ciba) added at 0.06 wt % on total furnish solids. Handsheetswere prepared at 80 gm⁻² and tested for burst and tensile strength,bulk, Bendtsen porosity, reflectance at 457 nm (ISO brightness), andopacity. Three loadings were obtained and results (Table 14)interpolated to a loading level of 30 wt %.

TABLE 14 Handsheet results Burst Tensile Bendsten index index porosityBulk cm³ Brightness % Opacity Filler Nm g⁻¹ Nm g⁻¹ cm³ min⁻¹ g⁻¹ F8 F10Unfilled 57.6 59.8 757 1.57 86.8 74.1 Control 13.0 18.5 1800 1.53 91.688.0 60-2 μm GCC Ex 29 18.0 23.5 500 1.45 91.5 89.1 2500 kW Ex 29 17.021.5 650 1.42 91.4 89.1 5000 kW Ex 30 24.0 27.5 130 1.40 91.4 90.2 3750kW Ex 30 25.0 27.5 130 1.38 91.3 90.2 5000 kW

The above results show that the co-ground fillers give increasedstrength, reduced porosity and increased opacity without detriment tothe brightness, all desirable properties. Using fillers from Example 30containing 11.7% co-ground fibre, the increase in strength is sufficientto allow the loading of filler to be increased from wt % using standardGCC filler to 40 wt % without loss of burst strength.

Example 32

321 g of a 72 wt % slurry of filler kaolin (WP, Imerys) was weighed intoa grinding pot. 105.9 g of wet unbleached North American kraft pine pulpat 10.9 wt % solids was then mixed in together with an additional 266cm³ water. 1485 g Carbolite 16/20 media was added and the mixture groundat 1000 rpm using a work input of 250 kWh/I expressed on drymineral+pulp. The fibre content of the dry product after separation on a700 μm screen was 3.9 wt % on the mineral measured by ignition at 950°C. The mean particle size (d₅₀) of the fibre was estimated at 83 μmusing a Malvern Mastersizer.

Example 33

206 g of a 72 wt % slurry of filler kaolin (WP. Imerys) was weighed intoa grinding pot. 108.7 g of wet unbleached North American kraft pine pulpat 10.9 wt % solids was then mixed in together with an additional 326cm³ water. 1485 g Carbolite 16/20 media was added and the mixture groundat 1000 rpm using a work input of 400 kWh/I expressed on mineral+pulp.The fibre content of the dry product after separation on a 700 μm screenwas 6.2 wt %. The mean particle size (d₅₀) of the fibre was estimated at95 μm using a Malvern Mastersizer.

The host pulp for this study was the same batch of unbleached NorthAmerican kraft pine pulp used in Examples 32 and 33. This was used asreceived from the manufacturer, diluting with water as required.Retention aid was Percol 292 (Ciba) added at 0.14 wt % on total furnishsolids.

Handsheets were made at a target weight of 160 gm·2 with a target fillerloading of 5 wt %. The sheets were pressed twice, and dried using aheated drum dryer, and conditioned for 12 hours at 50% RH and 23 C. Asample of the WP kaolin slurry was used as the control.

The sheets were tested for tensile strength, and clay content by ash.The results are set forth in Table 15 below:

TABLE 15 Linerboard results Loading Tensile index Filler wt % (Nm g⁻¹)Unfilled 0 33.0 WP control 4.4 23.1 Ex 32 3.9 31.1 Ex 33 3.7 29.4

The above results show that the co-ground kaolin filler has considerablyless weakening effect than unmodified kaolin in linerboard furnishesbased on unbleached kraft pulp.

Example 34

400 g of unrefined bleached softwood kraft pulp was soaked in 20 litresof water for 6 hours, then slushed in a mechanical mixer. The stock soobtained was then poured into a laboratory Valley beater and refinedunder load for 28 mins to obtain a sample of refined pulps beaten to 525cm³ Canadian Standard Freeness (CSF).

The pulp were then dewatered using a consistency tester (TestingMachines Inc.) to obtain a pad of wet pulp at between 13 and 18 wt %solids. This was then used in co-grinding experiments as detailed below:

Example 35

750 g of dry English kaolin (Intramax 60) was made into a slurry bymixing with 540 cm³ water and 1.9 g of a 40% solution of polyacrylatedispersant (Accumer 9300, Rohm & Haas). The pH was adjusted to 7 usingNaOH, and the final solids was 57.2 wt %. The slurry was thentransferred to a grinding pot and 37.5 dry g of the wet pulp preparedabove (Example 34) mixed with it. The pH was adjusted to 9 with NaOH and1500 g of Carbolite 16/20 grinding media added. The mix was groundtogether for 60 minutes with addition of water as required to maintainfluidity. After 60 minutes the temperature reached 55° C. The groundproduct was then separated from the media using screen of 700 μmaperture. The energy input was measured at 147 kWh/t, final solids was45.8 wt %, pH 9.2, and the dry product had a fibre content of 4.95 wt %expressed on total product. The modal particle size of the fibrecomponent was measured using a Malvern Mastersizer at 44 μm (e.s.d).

Example 36

750 dry g of Intramax 60 was weighed into a grinding pot as a 57 wt %slurry as prepared above (Example 34). 37.5 dry g of the wet pulp wasadded and the pH was then adjusted to 4.0 using 10% orthophosphoricacid. 1500 g Carbolite 16/20 media was then added and the mix ground for60 mins, after which time the temperature had reached 54° C. The workinput was 140 kWh/t. The slurry was separated as before and the finalsolids was 42 wt %. The pH was 5.3. The fibre content of the product wasmeasured at 4.0 wt %. Surprisingly, the modal particle size of the fibrecomponent was measured using a Malvern Mastersizer at 0.50 μm (e.s.d),almost an order of magnitude finer than at pH 9. This unexpectedobservation suggests that grinding under acid conditions is much moreeffective than under alkaline conditions.

Example 37

750 g dry marble flour was placed into a grinding pot with 400 cm³ waterand ground for 57 minutes with a work input of 120 kWh/t. The productwas shown to have 58 wt % of particles <2 μm esd, by Sedigraph. 37.5 dryg of wet pulp (as prepared in Example 34) was then mixed and the grindcontinued for a further 2 hours with the addition of 800 cm³ furtherwater and the expenditure of a further 313 kWh/t. The final temperaturewas 74° C., solids 37.4 wt %, and the fibre content of the dry productafter separation on a 700 μm screen was 4.4 wt %. The modal particlesize of the fibre was estimated at 50 μm using a Malvern Mastersizer.

Example 38

750 dry g of Optical HB (scalenohedral PCC) as a 34% solids slurry wasmixed with 37 g dry wt of wet pulp (as prepared in Example 34) and 200cm³ of water and 1500 g Carbolite 16/20 media added. The mixture wasground for 1 hour, using 154 kWh/t. The final temperature was 53° C. andafter separation of the media the slurry had a solids content of 41 wt %and the dried product had a fibre content of 5.3 wt %. The modalparticle size of the fibre component was between 100 and 200 μm byMalvern Mastersizer.

Example 39

Newsprint Study

These fillers were further compared in a handsheet study. The host pulpfor these fillers was prepared by slushing a Northern Europeanthermo-mechanical pulp sample. Since the pulp as received had a CSF of50 cm³, no further refining was done. Retention aid was Percol 292(Ciba) added at 0.02 wt % on total furnish solids. Handsheets wereprepared at 50 gm−2 and tested for burst and tensile strength, bulk,Bendtsen porosity, reflectance at 457 nm (ISO brightness), and opacity.Three loadings were obtained and the results (see Table 16) areinterpolated to a loading level of 10 wt %.

These results show that the co-ground fillers, especially with Intramax,give increased strength, and reduced porosity, all desirable properties,compared to the control fillers. Brightness and opacity are onlyslightly reduced. With Intramax, the increase in strength is sufficientto allow the loading of filler to be increased from 0 wt % to at least 8wt % with co-ground filler without loss of strength. The filled paperwould have lower porosity, and increased brightness and opacity.

TABLE 16 Handsheet results: newsprint, 10 wt % filler loading BurstTensile Bendsten index index porosity Bulk cm³ Brightness % OpacityFiller Nm g⁻¹ Nm g⁻¹ cm³ g⁻¹ g⁻¹ F8 F10 Unfilled 26.4 41.6 63 1.95 71.181.6 Control 20.5 38.0 60 1.87 72.7 85.7 Intramax Ex 35 24.0 41.0 461.84 71.8 85.2 Ex 36 24.5 40.0 46 1.85 71.5 85.4 Control 19.0 32.0 981.95 75.3 86.8 GCC Ex 37 20.0 35.5 88 1.93 74.8 86.5 Control 19.9 33.3153 2.00 75.7 87.6 OCHB Ex 38 21.0 35.5 90 1.93 75.8 88.0

Example 40

Supercalendered Magazine Paper Study

A handsheet study was carried using the same pulp as in the newsprintstudy. The time sheets were made at 55 gm−2, with filler loadingscovering the range from 30 to 40 wt %. Due to the higher loadings, theretention aid dose was increased to 0.07 wt % Percol 292. Handsheetswere tested for burst and tensile strength, bulk, Bendtsen porosity,reflectance at 457 nm (ISO brightness), and opacity. Three loadings wereobtained and the results (see Table 17) are interpolated to a loadinglevel of 32 wt %.

TABLE 17 Handsheet results: SC magazine, 32 wt % filler loading BurstTensile Bendsten index index porosity Bulk Brightness % Opacity FillerNm g⁻¹ Nm g⁻¹ cm³ g⁻¹ cm³ g⁻¹ F8 F10 Unfilled 25.6 45.2 59 1.95 70.482.3 Control 11.0 18.4 71 1.66 76.2 91.4 Intramax Ex 35 13.4 22.0 581.63 76.1 91.4 Ex 36 12.2 22.5 57 1.61 75.9 91.4 Control 11.1 17.2 2101.74 79.8 89.9 GCC Ex 37 12.0 19.7 150 1.73 79.8 90.0

These results show that increased strength, reduced porosity, andsimilar brightness and opacity are obtained using co-ground fillers. Inthe case of Intramax, the loading could be increased from 30 wt % to atleast 36 wt % without loss of strength, with reduced porosity andincreased brightness and opacity.

Example 41

Handsheet Study

The host pulp for this study was a batch of bleached chemical kraftsoftwood pulp which was slushed at 2% consistency and beaten in a Valleybeater to a CSF of 520 cm³. Retention aid was Percol 292 (Ciba) added at0.02 wt % on total furnish solids.

Two sets of sheets were made using scalenohedral precipitated calciumcarbonate (Optical HB, Imerys) at 25 (Set A) and 32 wt % (Set B) loadinglevels. A further set of sheets (Set C) were made at a loading of 25 wt% Optical HB+7 wt % of co-ground GCC from Example 37, so that the totalloading was 32 wt %. A control set (Set D) was made at a loading 25 wt %Optical HB+7 wt % of a standard GCC of 60% <2 um. A final set (Set E)was made using a 50/50 blend of Optical HB and co-ground GCC fromExample 37 so that the total loading was 31 wt %.

Handsheets were prepared at 80 gm⁻¹, pressed twice, and dried using aheated drum dryer, and conditioned for 12 hours at 50% RH and 23° C. Thesheets were tested for tensile strength, bulk, Bendtsen porosity,reflectance at 457 nm (ISO brightness), and opacity. The results are setforth in the Table 18 below:

These results show that the co-ground GCC filler can be used to increasefurther the filler loading of PCC-filled sheets with lower loss instrength than if only PCC was used. At the higher loadings, opticalproperties are maintained and porosity is reduced without serious lossof bulk.

TABLE 18 PCC top up results Tensile Bendsten % Opacity index porosityBulk Brightness F10 Filler Nm g⁻¹ cm³ g⁻¹ cm³ g⁻¹ F8 (80 gm⁻²) Unfilled66.6 213 1.50 84.0 73.8 Set A 25.3% 29.4 1131 1.63 90.0 89.4 Optical HBSet B 31.7% 21.6 1420 1.62 90.8 90.7 Optical HB Set C 32.5% 25.0 9921.57 90.8 90.8 OHB + Ex 37 Set D 31.6% 24.0 1123 1.58 90.8 90.6 OHB +Control GCC Set E 30.9% 26.2 824 1.53 90.5 90.2 50/50 OCB/Ex 37

Example 41

Samples were prepared using a laboratory vertical stirred media millequipped with a cylindrical, un-baffled grinding vessel of internaldiameter—14.5 cm. The mill was equipped with a vertical impeller havinga circular cross section shaft of 1.8 cm diameter. The shaft wasequipped with 4 impeller arms arranged in an X configuration at thebottom of the shaft. The impeller arms were of circular cross sectionand 1.8 cm diameter and were 6.5 cm long from shaft axis centreline totip.

Grinding media (Carbolite, Carbo Ceramics Inc., USA) was of 16/20 meshsize and had specific gravity 2.7.

Ground Calcium Carbonate (GCC) (Intracarb 60, IMERYS Minerals, Belgium)had a sedigraph particle size of 60% <2 μm.

Pulp was bleached kraft softwood (Botnia Pine RM90) beaten to 520 cm³CSF.

Lab grinds were based on 1.5 kg of grinding media, 500/0 Media VolumeConcentration (MVC), Pulp level of 5 wt. % of total solids, energy input2500 kWM of pulp and impeller speed 1000 rpm. Grinds were performed inbatch mode at a range of solids levels.

At the end of each grind the grinding chamber was removed from the milland the contents removed. The grinding media was then separated from theproduct external to the mill.

The conditions for each grind and the resultant product properties areshown below in Table 19. The 8100 viscosity is the viscosity measured ona Brookfield viscometer (Brookfield Viscometers Ltd, BrookfieldTechnical Centre, Stadium Way, Harlow, Essex CM19 5GX, England) at 100rpm.

TABLE 19 Filter paper Grinding B100 Pulp Fibre Modal fibre burstincrease solids viscosity content d₅₀ particle size Fibre test (%increase Sample (wt. %) (mPas) (wt. %) (μm) (μm) steepness in burst) 135 9600 4.6  87 89 30 20 2 27.5 4500 4.6 — 96 28 17 3 22.5 1850 4.3 138259 28 17 4 17.5 950 4.1 205 352 31 12 5 12.5 330 3.6 203 409 30 15

These data indicate:

-   -   The sample produced at the highest grinding solids has: the        highest viscosity, the highest pulp content, the finest MFC size        and the highest (best) filter paper burst increase test.    -   Samples produced at lower grinding solids have lower viscosity,        lower pulp content, coarser MFC size and lower filter paper        burst increase tests.    -   All of the samples have high viscosity compared to typical GCC        products where B100 viscosities of <200 mPas are typical.

Example 42

An attempt was made to produce a co-ground product in a full scale SMDequipped with a standard 250 urn screen (www.metso.com). The grindingmedia, GCC and pulp were the same as in Example 41 except that the pulpwas unrefined. The grinding media charge was 5 tonnes. The operatingconditions were also similar to those used in Example 41; 50% MVC, pulplevel of 5 wt. % of total solids, energy input 2500 kWh/t of pulp and avariety of impeller rpm to give a similar tip speed to that of the labmill. The grinds were performed in continuous open circuit mode.

Initially, grinding was attempted at 35 wt. % total solids as in Example41. However, it was not possible to produce any product under theseconditions. The high viscosity product would not flow through the screenand out of the mill. Instead the material built up in the mill. Thegrinding solids were lowered to less than 20 wt. % to obtain anacceptable flow through the mill and the products under these conditionsdid not show the same improvements in performance in paper as seen withthe higher solids grinding.

For example, Sample 1 in Example 41 was produced in a lab batch grind(50% MVC, pulp level of 5% of total solids, energy input 2500 kWh/t ofpulp and 1000 rpm impeller speed) at 35% solids. Samples 6 and 7 wereproduced in a full scale SMD equipped with a standard 250 μm screenunder similar conditions except that the solids were lowered to <20% inorder to achieve a flow through the mill.

TABLE 20 Modal fibre particle size Filler loading for Sample ID (um)Burst Index of 20 Nm/g 1 89 28 6 194 24 7 264 23.5 Lntracarb 60 — 20

These data show

-   -   Both the lab and full scale produced MFC allowed increased        filler loadings compared to the control.    -   However, the MFC produced in the lab batch grind at 35% solids        had finer fibre peak max and allowed a higher filler loading        than the sample produced in an SMD where the solids had to be        lowered to allow a flow through the mill    -   NB It was not possible to operate the SMD under the high solids        condition.

Example 43

Samples were prepared using a pilot scale vertical stirred media millequipped with a cylindrical, grinding vessel of internal diameter—87 cm.The mill was equipped with a vertical impeller having a circular crosssection shaft. The shaft was equipped with 4 impeller arms arranged inan X configuration at the bottom of the shaft. The impeller arms were ofcircular cross section and were 30 cm long from shaft axis centreline totip.

The grinder was operated in batch mode. GCC and pulp were the same as inExample 41. Tests were performed at 50% MVC, and 39% solids with a pulplevel of 5% of the total solids. The grinder rpm was 285. The pulp wasunbeaten. Two sets of tests were performed. The first utilised 16/20grinding media as in Example 41 and the second 3 mm media with the samedensity. The fibre d₅₀ and modal mineral particle size for both testsare shown in Table 21.

TABLE 21 Modal mineral Energy input Fibre d₅₀ (μm) particle size (μm)(kWh/t) 16/20 3 mm 16/20 3 mm 3750 73 61 1.61 1.94 5000 42 44 1.42 1.837500 15 27 1.01 1.61 10000 8 16 0.80 1.37

These data show that fibre grinding behavior was similar with coarsermedia especially at the lower energy inputs. However, mineral grindingwas significantly reduced by use of the coarser media.

Example 44

These tests were performed in the same pilot grinder as was used inExample 43. GCC and pulp were the same as in Examples 41 and 42.

A sample was prepared in batch mode under the following conditions andwith unbeaten pulp. Total solids 10%, pulp as percentage of total solids20%; MVC 50%; 285 rpm; 3 mm media; Energy input 3500 kWh/t pulp. Theresultant sample (sample 8) had a fibre d₅₀ of 102 μm.

In another test the same conditions were used but in this case thegrinder was configured in recirculating batch mode with a 250 um screen.The flow rates were unacceptable because of the high viscosity of theproduct and no product was obtained.

In a further test a sample was prepared with the grinder configured inrecirculating batch mode and a 1 mm screen was used and a high flow rateof 60 l/min was obtained. The resultant sample (sample 9) had a fibred₅₀ of 107 μm.

The two samples were used in a handsheet evaluation using the sameprocedure as in Example 42. Results are summarized in Table 22.

TABLE 22 Filler loading Fibre for 30% of Sample ID Configuration d₅₀(μm)unfilled burst 8 Batch 102 54 9 Recirculating 107 50 batch Intracarb 60— — 26

These data show that the use of coarse media and hence coarse screensallows the preparation of a co-ground product in a commercially viable,re-circulating batch (or continuous) configuration, despite the highviscosity of the product.

Example 45

Tests were performed in a pilot scale tower mill (Hosokawa Alpine modelANR 250). This is a vertical stirred media mill with an un-baffledcylindrical grinding chamber and a vertical impeller shaft equipped witha series of impeller rotor disks throughout its length. The mill isapproximately two thirds filled with grinding media. In operation feedenters the mill at the bottom and passes through the grinding zonebefore rising to a quiescent zone where the grinding media starts tosediment away from the product. The product then exits the mill via aclassifier wheel which serves to retain any further grinding mediawithin the mill.

A co-ground product was prepared in an open circuit continuousconfiguration under the following conditions and with unbeaten pulp.Total solids 12.4 wt. %; pulp as percentage of total solids 20%; averageMVC 22%; 500 rpm; 2-2.5 mm media of specific gravity about 6; Energyinput 3200 kWh/t pulp. Flow rate into the mill 1.7 l/min

Initial attempts to run under these conditions were unsuccessful sincethe grinding media was carried over into the product. (An earlierattempt using 1 mm media failed as well also because of media carryover).

Subsequently a water addition of approx. 1 l/min was made immediatelybefore the classifier wheel reducing the solids of the product exitingthe mill to 8.1 wt %. Under these conditions all the media was retainedin the mill.

The resultant sample (sample 10) had a fibre d₅₀ of 145 μm and a modalfibre particle size of 89 μm and was evaluated in a handsheet evaluationusing the same procedure as in Example 42. Results are summarized inTable 23.

TABLE 23 Fibre Modal Fibre Filler loading d₅₀ particle size for 30% ofSample ID Configuration (μm) (μm) unfilled burst 10 Tower mill 145 89 49with coarse dense media and water addition before classifier Intracarb60 — — 25

These data show that the use of coarse dense media and water additionimmediately before the classifier wheel in a tower mill allows thepreparation of co-ground in a, commercially viable configuration despitethe high viscosity of the product.

Example 46

Samples are prepared using a laboratory vertical stirred media millequipped with a cylindrical, un-baffled grinding vessel of internaldiameter—14.5 cm. The mill is equipped with a vertical impeller having acircular cross section shaft of 1.8 cm diameter. The shaft is equippedwith 4 impeller arms arranged in an X configuration at the bottom of theshaft. The impeller arms are of circular cross section and 1.8 cmdiameter and are 6.5 cm long from shaft axis centreline to tip.

Grinding media (Carbolite, Cart>o Ceramics Inc., USA) is 16/20 mesh sizehaving a specific gravity of 2.7.

Pulp is bleached kraft softwood (Botnia Pine RM90) beaten to 520 cm³CSF.

Lab grinds are based on 1.5 kg of grinding media, 50% Media VolumeConcentration (MVC) which may be varied, pulp levels cover theconsistency range up to 10 wt. %, Energy inputs of up to 20 000 kWh/t ofpulp are investigated using an impeller speed of 1000 rpm. Grinds areperformed in batch mode at a range of solids levels.

At the end of each grind the grinding chamber would be removed from themill and the contents removed. The grinding media is separated from theproduct external to the mill.

The MFC products are characterised for particle size using a Malvernlight scattering device, for B100 viscosity using a Brookfieldviscometer (Brookfield Viscometers Ltd, Brookfield Technical Centre,Stadium Way, Harlow, Essex CM19 5GX, England) at 100 rpm and the paperperformance evaluated using the filter paper burst increase test and thehandsheet method of Example 7 except that no filler is used or else thefiller is Intracarb 60 (Imerys, Belgium).

The expectation is that the MFC produced gives increased filter paperburst tests and stronger hand sheets. It is envisaged that higherconsistency and higher energy processing favour finer MFC and that theremay be an optimum MFC size for paper strength performance. The optimumperformance will, likely, be obtained most efficiently by processing athigh consistency.

Example 47

Samples are prepared using a pilot scale vertical stirred media millequipped with a cylindrical, grinding vessel of internal diameter 87 cm.The mill is equipped with a vertical impeller having a circular crosssection shaft. The shaft is equipped with 4 impeller arms arranged in anX configuration at the bottom of the shaft. The impeller arms are ofcircular cross section and are 30 cm long from shaft axis centreline totip.

The grinder is operated in batch mode. Pulp is the same as in Example46. Tests are performed under optimised conditions from Example 46.Grinder rpm is about 285. The pulp is unbeaten. Two sets of tests areperformed. The first utilising 16/20 grinding media as in Example 46 andthe second 3 mm media with the same density.

The MFC produced is characterised and evaluated using the method ofExample 46.

It is envisaged that both grinding media would give similar psd MFC andthat these MFC samples will allow production of handsheets withincreased strength

Example 48

Tests are performed in the same pilot grinder as was used in Example 42.Pulp is the same as in Example 45. The grinding media is 3 mm.

A MFC sample is prepared in batch mode under the optimised conditionsfrom Example 45. The MFC psd properties of the resultant sample will bedetermined.

In another test the same conditions would be used but in this case thegrinder would be configured in recirculating batch mode with a 250 umscreen. The flow rates would probably be unacceptable because of thehigh viscosity of the product and no product would be obtained.

In a further test a sample is prepared with the grinder configured inrecirculating batch mode and a 1 mm screen is used and a high flow rateis expected.

The MFC produced is characterised and evaluated using the method ofExample 45.

It is expected that the data will show that the use of coarse media andhence coarse screens allows the preparation of fine psd MFC at highconsistency and low energy in a, commercially viable, re-circulatingbatch (or continuous), configuration despite the high viscosity of theproduct.

Example 49

Tests are performed in a pilot scale tower mill (Hosokawa Alpine modelANR 250). This is a vertical stirred media mill with an un-baffledcylindrical grinding chamber and a vertical impeller shaft equipped witha series of impeller rotor disks throughout its length.

The mill is approximately two thirds filled with grinding media. Inoperation, feed enters the mill at the bottom and passes through thegrinding zone before rising to a quiescent zone where the grinding mediastarts to sediment away from the product. The product then exits themill via a classifier wheel which serves to retain any further grindingmedia within the mill.

A MFC sample is prepared in an open circuit continuous configurationunder the optimised conditions from Example 46 and with unbeaten pulp.2-2.5 mm grinding media of specific gravity about 6 is used. Energyinputs in the range 2000-15000 kWh/t pulp would are used.

It is expected that initial attempts to run under these conditions wouldbe unsuccessful due to the grinding media being carried over into theproduct because of the high viscosity of the MFC.

Subsequently a water addition is made immediately before the classifierwheel reducing the solids of the product exiting the mill to a levelwhere the media is not carried over. Under these conditions all themedia is retained in the mill.

The MFC produced is characterised and evaluated using the method ofExample 46.

The resultant sample will have a fine fibre psd. Evaluations in handsheets will indicate that the MFC produced gave increases in burststrength of the sheets.

These data indicate that the use of coarse dense media and wateraddition immediately before the classifier wheel in a tower mill allowsthe preparation of MFC in a, commercially viable configuration despitethe high viscosity of the product.

Ultrasonic Treatment of MFC

Example 50

The effect of an ultrasonic bath on various microfibrillated celluloseand microfibrillated cellulose and inorganic particulate materialproduct forms.

The first study was to investigate the effect of using a laboratoryFisher brand FB11005 ultrasonic water bath on various microfibrillatedcellulose and inorganic particulate material product forms. Themicrofibrillated cellulose and inorganic particulate material productform was a 50 POP (percentage of pulp) IC60/Botnia (i.e., a 1:1 ratio)mixture of in the form of a slurry, belt pressed cake and a high solidsdried 50 wt. % solids product. IC60 is a fine ground calcium carbonateavailable as Intracarb 60 from Imerys Minerals Limited. The samples werediluted to make a 20% POP (Percentage Of Pulp—The POP or Percentage ofPulp is the percentage of the dry weight of the sample that is pulp orfibrils rather than inorganic particulate material) suspension at 6.25wt. % solids. Each sample was subjected to various times within theultrasonic bath and then subjected to 1 minute on the laboratorySilverson mixer at 7500 rpm; subsequent FLT (Nm/g: measurement oftensile strength) and viscosity measurements were made.

The FLT index is a tensile test developed to assess the quality ofmicrofibrillated cellulose and re-dispersed microfibrillated cellulose.The POP of the test material is adjusted to 20% by adding whicheverinorganic particulate was used in the production of the microfibrillatedcellulose/inorganic material composite (in the case of inorganicparticulate free microfibrillated cellulose then 60 wt. %<2 um GCCcalcium carbonate is used). A 220 gsm sheet is formed from this materialusing a bespoke Buchner filtration apparatus. The resultant sheet isconditioned and its tensile strength measured using an industry standardtensile tester.

FIG. 2 shows the effect upon the viscosity of the microfibrillatedcellulose and inorganic particulate material slurries. It can be seenthat within the first 5 minutes a small increase in the viscosity wasobserved. Tables 24-27 show strength properties of the microfibrillatedcellulose and inorganic particulate material composition afterultrasonic bath treatment. It can be seen that the strength of thematerials as measured by the FLT Index method have not changedsignificantly. The use of the ultrasonic bath for the re-dispersion ofthe microfibrillated cellulose and inorganic particulate materialcompositions for improvements in quality is not recommended. The lowpower input does not affect the strength properties but does influencethe viscosity slightly.

TABLE 24 Slurry properties Time in US Viscosity FLT Index Sample bathmins mPas Nm/g 50 POP IC60/ 0 1820 9.4 Botnia slurry 1 1940 8.7 2 19208.6 3 1920 8.7 4 1820 8.5 5 1820 8.8 10 1660 8.9 20 1520 9.0

TABLE 25 Belt pressed cake properties Time in US Viscosity FLT IndexSample bath mins mPas Nm/g 50 POP IC60/Botnia 0 1240 7.7 belt press cake1 1280 8.2 2 1360 8.2 3 1360 8.1 4 1360 8.5 5 1300 8.0 10 1320 7.4 201340 7.5

TABLE 26 High solids dried 50 wt % properties Time in Viscosity FLTIndex Sample US bath mPas Nm/g 50 POP IC60/Botnia 0 1540 9.0 product@50% solids 1 1600 8.2 2 1660 9.1 3 1720 8.9 4 1700 9.1 5 1680 9.2 101480 9.0 20 1600 9.3

TABLE 27 High solids dried 60 wt % properties Time in Viscosity FLTindex Sample US bath mPas Nm/g 50 POP IC60/Botnia 0 1100 6.8 product @60% solids 1 1220 7.3 2 1020 7.2 3 1100 6.7 4 1100 6.8 5 1180 6.7 101120 7.0 20 1100 6.9

Example 51

The effect of an ultrasonic probe on microfibrillated cellulose andinorganic particulate material slurry.

This experiment was to explore the effect that an ultrasonic probe hasupon a microfibrillated cellulose and inorganic particulate materialslurry. The ultrasonic probes used were “Sonics Vibracell VCX500 500Watt model” with a “Probe horn CV33” and were used for the dispersion ofmineral slurries prior to particle size measurement. The probe (horn) isspecifically designed to operate at an amplitude of 40% but for this andfurther experiments it has been operated up to 100%.

The 50% POP IC60/Botnia (1:1 ratio) slurry at a total solids content of1.7 wt. % was diluted to 20% POP with an IC60 ground calcium carbonate(70 wt. % solids) slurry. This made the total solids of the samples 4.24wt. %.

The ultrasonic probe was immersed into the slurry and was subjected tovarious times of ultrasound at various amplitudes. FIGS. 3 and 4highlight the increase in FLT Index (Nm/g: measurement of tensilestrength) and viscosity. It can be seen in the figures that the higherthe amplitude the greater the increase in tensile strength. At 100%amplitude a 20% increase in FLT Index can be achieved within 30 secondscompared to the original slurry. Compared to the original slurry a 33%increase within 2 minutes of applied ultrasound can be achieved. At thereduced amplitude of 65%, the increase in FLT Index was 14% after 2minutes of ultrasound compared to the feed slurry.

Example 52

The effect of pulsed ultrasound on microfibrillated cellulose andinorganic particulate material slurry.

The ultrasonic probe can be operated in a continuous mode or pulsedmode. This experiment was to look at this effect. The microfibrillatedcellulose and inorganic particulate material slurries were prepared asin Exp. 51, above and subjected to pulsed ultrasound. FIG. 5 shows thatan increase in FLT Index can be made using the pulsed mode of operation.The use of the ultrasonic probe for the enhancement of themicrofibrillated cellulose and inorganic particulate material improvesproduct quality. The significant increase of the microfibrillatedcellulose and inorganic particulate material slurry properties can beachieved preferably using a high amplitude and run in a continuous mode.

Example 53

The effect of ceramic grinding media on ultrasound efficiency within amicrofibrillated cellulose and inorganic particulate material slurry.

The production of a microfibrillated cellulose and inorganic particulatematerial product is achieved by the wet attrition milling of celluloseand mineral in the presence of a ceramic grinding media. This experimentwas performed to investigate the effect of an ultrasonic process withsome of ceramic grinding media present. Slurries of microfibrillatedcellulose and inorganic particulate material as prepared in Examples 51and 52, above were doped with 10 ceramic grinding media beads (˜3 mmsize). The materials were subjected to various energy inputs at 100%amplitude. FIG. 6 shows that the presence of the media in the sample hasno detrimental effect on the increase in FLT Index. The presence of theceramic grinding media has no effect on the ultrasonic processing of themicrofibrillated cellulose and inorganic particulate material slurryunder these conditions.

Example 54

The effect of an ultrasonic probe microfibrillated cellulose andinorganic particulate material, 50% POP belt pressed cake.

A 50% POP IC60/Botnia belt press cake was the feed material for thisstudy. The belt pressed cake was diluted to 20% POP, 6.25 wt. % solidsusing IC60 ground calcium carbonate slurry. Samples were made andsubjected to:

i) 1 minute of high shear mixing on the Silverson mixer: The control

ii) Various times of ultrasound at 100% amplitude.

FIG. 7 shows that the belt pressed cake can be re-dispersed in waterusing the ultrasonic probe and the control FLT Index can be achieved andsurpassed.

Example 55

The effect of an ultrasonic probe on microfibrillated cellulose mineralfree (no inorganic particulate material used in the fibrillationprocess) belt pressed cake.

To further explore the re-dispersion of a belt pressed cake, a mineralfree version was evaluated. The belt pressed cake was diluted to 20%POP, 6.25 wt. % solids using IC60 ground calcium carbonate slurry.Samples were made and subjected to:

i) 1 minute of high shear mixing on the Silverson mixer: The control

ii) Various times of ultrasound at 100% amplitude.

FIG. 8 highlights once again that ultrasonics alone can achieve thesample properties that are produced with high shear mixing. High shearmixing combined with ultrasonics can yield an improved tensile strength.

Example 56

The effect of an ultrasonic probe on 60 wt. % a high solids driedmicrofibrillated cellulose and inorganic particulate material slurry.

A development product that is produced by drying a belt pressed cake wasevaluated with the use of ultrasonics. This 50% POP IC60/Botnia 60 wt. %solids material requires 3 to 4 minutes of high shear Silverson mixingto achieve a FLT index of 9 Nm/g.

This Study Explored

i) The use of ultrasound as a pre cursor to high energy mixing

ii) The use of ultrasound as an additional aid to improve FLT values

FIG. 9 shows that the effects of the ultrasonic energy is more effectiveutilised post high shear mixing. FIG. 10 demonstrates the benefits ofhigh shear mixing and ultrasonics combined. The use of ultrasonics isdemonstrated to be an efficient way to re-disperse driedmicrofibrillated cellulose and inorganic particulate material producteither with or without high shear mixing.

The results of Examples 50-56 show at least the following unexpectedresults of adding ultrasonic processing to microfibrillated cellulose ormicrofibrillated cellulose and inorganic particulate materialproduction:

-   -   A microfibrillated cellulose or microfibrillated cellulose and        inorganic particulate material slurry's properties can be        substantially enhanced by ultrasonification if applied        preferably by a probe or an ultrasonic water bath    -   A higher amplitude yields a higher FLT Index    -   Ceramic contaminants within a microfibrillated cellulose or        microfibrillated cellulose and inorganic particulate material        slurry has no detrimental effect upon the ability of the        ultrasound to affect the slurry's properties beneficially    -   A microfibrillated cellulose or microfibrillated cellulose and        inorganic particulate material belt press cake is very amenable        to ultrasonics as a way to re-disperse it    -   Ultrasonics can either replace high shear re-dispersion or        enhance the procedure    -   Higher solid content materials can be re-dispersed using        ultrasonics.

Example 57

The following trials were carried out to evaluate the properties ofmicrofibrillated cellulose and inorganic particulate material that hadbeen fibrillated and then dewatered, dried and pelletized to produce anapproximate 50% solids concentration. The dried microfibrillatedcellulose and inorganic particulate material composition was then madedown to various fiber slurry concentrations between 07% and 3.4%. Thefibrillated cellulose and inorganic particulate material. (mineral)product was a 50% percentage of pulp (POP) aqueous composition producedby fibrillating a mixture of 50% POP Botnia pulp/ground calciumcarbonate IC60 (i.e., a 1:1 wt. ratio) in the form of a slurry. Theoverall solids of the pelletized product used was 50 wt. %. Theoperating pressure for the sonication trials was varied from 0 to 4 barpressure to determine the optimum pressure for sonication. The trialswere carried out at different temperatures (20° C. to 50° C.) todetermine the optimal process temperature. Cooling water at various flowrates was pumped into a flow cell cooling jacket and used to maintainthe operating temperature at the required level.

The microfibrillated cellulose and inorganic particulate materialsslurry was subjected to grinding in a stirred media detritor. The slurrywas screened using two screening stages through slotted screens of 250microns and 120 microns, respectively. The microfibrillated celluloseand inorganic particulate material slurry was dewatered using a beltpress followed by further drying in an air swept Atritor dryer & mill(available from Atritor Limited, 12 The Stampings, Blue Ribbon Park,Coventry, West Midlands, England). An Atritor mill is an air-swept millor dryer having the capability to introduce a stream of hot air fordrying and milling materials, in order to process and dry themicrofibrillated cellulose and inorganic particulate material (e.g.,calcium carbonate) composition utilized in the trials. Other equivalentair swept dryer and mills are known to one of ordinary skill in the art.

The feed solids to the belt press was 2 wt. % of the 50 wt. % POPslurry. The feed solids to the Atritor dryer and mill was 30 wt. % at abulk density of 0.5 kg/L. The inlet temperature of the Atritor mill wasset at 150-170° C. and the outlet temperature of air was measured as68-75° C. Product solids content of the dried microfibrillated andinorganic particulate material product was 50 wt. %. The dried materialwas thereafter fed into a Kahl pellet mill with an inlet and outlettemperature of 16° and thereby pelletized.

The ultrasonic unit used in the trials was a Hielscher UIP1000hdindustrial scale ultrasonic processor available from HielscherUltrasonics GmbH (Oderstr. 53 D-14513 Teltow, Germany and 530 RingwoodAve. Lembo & Gray Bldg. Wanaque, N.J. 07465, USA).

The test material was recirculated from a feed tank to the ultrasonicflow cell. The volume in the feed tank was 2.5 L. The flow rate duringall trials was maintained at approximately 1.5 L/min. A progressivecavity pump was used for pumping. 250 ml samples were taken after 0, 1,2, 4 and 10 minutes.

All samples collected from trials, which used made-down pelletizedmicrofibrillated cellulose and inorganic particulate material as feed,were assessed for nibs using the TAPPI dirt count method. Nibs areagglomerates in the microfibrillated cellulose and inorganic particulatematerial tensile (FLT) sheet that would not have been broken down orde-agglomerated after processing.

Based on the recommendations from the ultrasonic supplier, all thetrials were conducted using the largest booster (B4-2.2) and BS4d22sonotrode.

Once the optimum pressure and temperature were identified, trials atdifferent fiber solids, i.e. 0.7%, 1.5%, 2.5% and 3.3% were carried out.Thus, the optimum fiber solids for sonication were identified.

Example 58: Optimization Trials—Effect of Pressure

These trials were conducted using handmade-down pellets (low energy).The pellets were made using microfibrillated cellulose and inorganicparticulate material dried in an air swept Atritor dryer and mill. Themicrofibrillated cellulose and inorganic particulate material was testedat 50% solids and 50% POP (Botnia pulp/ground calcium carbonate IC60).The objective was to re-disperse and de-agglomerate pelletizedmicrofibrillated cellulose and inorganic particulate material (exceptwhere otherwise indicated) using sonication and to recover the productquality in terms of FLT index and nibs of the initial slurry productbefore being dewatered, dried and pelletized. The made down pellets werediluted to 6.6% total solids (3.3% fiber solids) and sonication trialswere carried out in recirculation mode at the different pressures (0 to4 bar). Results from these trials are presented in FIGS. 11A to C.

Overall FLT index did not show a significant difference when processingat higher pressures; but from a scaling point of view, it was importantto ensure that the ultrasonic unit was drawing as much power as possibleduring the processing of microfibrillated cellulose and inorganicparticulate material. The average power draw vs. processing time chartshows that the optimum pressure was 3 bar.

Example 59: Optimization Trials—Effect of Temperature

These trials were conducted using handmade-down pellets (low energyinput). The made down pellets were diluted to 6.6% total solids (3.3%fiber solids) and sonication trials were carried out in recirculationmode at the different temperatures (20° C. to 50° C.). Processingtemperature was controlled by adjusting the flow rate of the coolingwater in the flow cell water jacket. Results from these trials are shownin FIGS. 12 A to C.

FLT index showed no significant difference at the different temperaturesassessed. Operating at lower temperatures results in higher power drawfrom the ultrasonic unit, which is preferable. Therefore, it is wasdemonstrated that 20° C. is an optimal temperature when sonicatingmicrofibrillated cellulose.

Example 60: Trials Using Product that has been Made Down Using aLaboratory High Shear Mixer

Pelletized microfibrillated cellulose and inorganic particulatematerial, as described in Example 57, was made down using a laboratorySilverson high shear mixer. About 200 kWh/t of energy was used duringthe make down. Trials were carried out in recirculation mode. Unlike inprevious trials the high shear product was not recirculated for 30 minbefore sonication trials began. The high shear product was sonicated atdifferent fiber solids, see FIGS. 13A and B.

Similar to trials reported earlier, the optimum energy was about 2000kWh/t. As depicted in FIGS. 13 A and B, sonicating at lower solids (0.7%and 1.5%) gave the best products in terms of FLT index and viscosity.

Example 61: Post Treatment Trials Using Continuous GroundMicrofibrillated Cellulose and Inorganic Particulate Material Slurry

Microfibrillated cellulose and inorganic particulate material slurry wasobtained pressure screening (i.e., never dewatered or dried product).Trials were carried out to determine the effectiveness of sonication inpost treating microfibrillated cellulose and inorganic particulatematerial slurry after the grinding process. Data on the trials ispresented in FIGS. 14 A to C.

There was an increase in FLT and viscosity in these trials, which is anindication of improved product quality. Processing at lower solids givesbetter products at a given energy input. The energy required to giveacceptable product improvement is high, i.e., more than 1000 kWh/t,which makes ultrasonic technology more energy intensive in post treatingmicrofibrillated cellulose and inorganic particulate material slurry,though product performance is enhanced.

Example 62: Post Treatment Trials Using Refiner Product

Pelletized microfibrillated cellulose and inorganic particulatematerial, prepared in accordance with the procedures of Example 57, wasmade down using a pilot pulper and subsequently refined using a pilotrefiner. The product from the refiner was collected and trials werecarried out to investigate the effect of sonication. Trials were done at3 solids levels—1.5%, 2.5% and 3.3% fiber solids. The data is reportedin FIGS. 15 A to C.

Improvement in product quality was shown by the increase in FLT indexand viscosity. The energy required to increase the FLT by 1.0 was about2000 kWh/t. Post treatment of refiner product using sonication was veryenergy intensive.

Example 63: Post Treatment of Mineral Free Microfibrillated Celluloseand Mineral Free Microfibrillated Cellulose Subjected to an AdditionalPass Through a Homogenizer as Well as an Ultrasonic Treatment Step

Mineral free (100% POP/Birch pulp microfibrillated cellulose wasproduced in a pilot stirred media detritor (Supermill) grinder usinghigh density zirconia media (specific gravity of 6). The mineral freeproduct, composed of mostly cellulose (organic matter) was passedthrough a pilot homogenizer to produce a more finely fibrillated,mineral free, microfibrillated cellulose. Trials were then carried outto determine the effect of sonication on mineral free microfibrillatedground product with and without a homogenization step. The data on thesetrials is reported in FIGS. 16A and B.

The data in FIGS. 16A and B indicate that it is possible to producemicrofibrillated cellulose from mineral free grinder product (birch)using sonication and without a homogenization step. The FLT ofmicrofibrillated cellulose subjected to a homogenization step is greaterthan 15 Nm/g. The trials reported in FIGS. 16A and B after sonicatingthe mineral free ground product up to about 1500 kWh/t produced a groundmicrofibrillated cellulose with FLT indices and d₅₀ particle sizes inthe range of ground microfibrillated cellulose subjected to ahomogenization step.

Additional Embodiments of the Invention

The Examples set forth above and the Embodiments set forth below areillustrative of the many embodiments of the invention disclosed hereinby the inventors and are not intended to be limitations of theinvention.

Embodiment 1

A method for preparing an aqueous suspension comprising microfibrillatedcellulose and inorganic particulate material with enhanced viscosity andtensile strength properties, the method comprising a step ofmicrofibrillating a fibrous substrate comprising cellulose in an aqueousenvironment in the presence of an inorganic particulate material toproduce an aqueous suspension comprising microfibrillated cellulose andinorganic particulate material, and further comprising subjecting theaqueous suspension comprising microfibrillated cellulose and inorganicparticulate material to sonication to produce the aqueous suspensioncomprising microfibrillated cellulose and inorganic particulate materialwith enhanced viscosity and tensile strength properties.

Embodiment 2

The method according to embodiment 1, wherein the microfibrillating stepcomprises grinding the fibrous substrate comprising cellulose in thepresence of the inorganic particulate material in a grinding vessel.

Embodiment 3

The method according to embodiment 2, further comprising an initial stepof grinding the inorganic particulate material in the absence of thefibrous substrate comprising cellulose to obtain an inorganicparticulate material having a desired particle size.

Embodiment 4

The method according to embodiment 1, wherein said sonication isconducted with one or more devices selected from a group consisting ofan ultrasonic probe, an ultrasonic water bath, an ultrasonichomogenizer, an ultrasonic foil and an ultrasonic horn.

Embodiment 5

The method according to embodiment 1, wherein said tensile strength ofthe aqueous suspension comprising microfibrillated cellulose andinorganic particulate material with enhanced viscosity and tensilestrength properties is increased by at least 5% over the aqueoussuspension comprising microfibrillated cellulose and inorganicparticulate material not subject to sonication.

Embodiment 6

The method according to embodiment 1, wherein said tensile strength ofthe aqueous suspension comprising microfibrillated cellulose andinorganic particulate material with enhanced viscosity and tensilestrength properties is increased by at least 10% over the aqueoussuspension comprising microfibrillated cellulose and inorganicparticulate material not subject to sonication.

Embodiment 7

The method according to embodiment 1, wherein said tensile strength ofthe aqueous suspension comprising microfibrillated cellulose andinorganic particulate material with enhanced viscosity and tensilestrength properties is increased by at least 20% over the aqueoussuspension comprising microfibrillated cellulose and inorganicparticulate material not subject to sonication.

Embodiment 8

The method according to embodiment 1, wherein said aqueous suspensioncomprising microfibrillated cellulose and inorganic particulate materialis subject to sonication at an energy consumption of up to 1000 kWh pertonne (kWht⁻¹) of dried fibrils.

Embodiment 9

The method according to embodiment 1, wherein said aqueous suspensioncomprising microfibrillated cellulose and inorganic particulate materialis subject to sonication at an energy consumption of up to 1500 kWh pertonne of dried fibrils.

Embodiment 10

The method according to embodiment 1, wherein said aqueous suspensioncomprising microfibrillated cellulose and inorganic particulate materialis subject to sonication at an energy consumption of up to 2500 kWh pertonne of dried fibrils.

Embodiment 11

The method according to embodiment 1, wherein said sonication is run incontinuous mode.

Embodiment 12

The method according to embodiment 1, wherein said sonication is run inpulse mode.

Embodiment 13

The method according to embodiment 1, wherein said aqueous suspensioncomprising microfibrillated cellulose and inorganic particulate materialis formed into semi-dry product prior to sonication.

Embodiment 14

The method according to embodiment 13, wherein said semi-dry product isformed into a belt-pressed cake prior to sonication.

Embodiment 15

The method according to embodiment 1, wherein said viscosity of theaqueous suspension comprising microfibrillated cellulose and inorganicparticulate material with enhanced viscosity and tensile strengthproperties is increased by at least 5% over the aqueous suspensioncomprising microfibrillated cellulose and inorganic particulate materialnot subject to sonication.

Embodiment 16

The method according to embodiment 1, wherein the sonication isperformed at an amplitude of up to 60%.

Embodiment 17

The method according to embodiment 1, wherein the sonication isperformed at an amplitude of up to 80%.

Embodiment 18

The method according to embodiment 1, wherein the sonication isperformed at an amplitude of up to 100%.

Embodiment 19

The method according to embodiment 1, wherein the fibrous substratecomprising cellulose is in the form of a pulp, for example, a chemicalpulp, or a chemithermomechanical pulp, or a mechanical pulp, or arecycled pulp, or a paper broke pulp, or a papermill waste stream, orwaste from a papermill, or combinations thereof.

Embodiment 20

The method according embodiment 1, wherein the inorganic particulatematerial is an alkaline earth metal carbonate or sulphate, such ascalcium carbonate, magnesium carbonate, dolomite, gypsum, a hydrouskandite clay such as kaolin, halloysite or ball clay, an anhydrous(calcined) kandite clay such as metakaolin or fully calcined kaolin,talc, mica, perlite or diatomaceous earth, or combinations thereof.

Embodiment 21

The method according to embodiment 1, wherein the inorganic particulatematerial is an alkaline earth metal carbonate, for example, calciumcarbonate.

Embodiment 22

The method according to embodiment 1, wherein the inorganic particulatematerial is kaolin.

Embodiment 23

The method according to embodiment 2, wherein the grinding vessel isselected from the group consisting of a tower mill and a stirred mediadetritor.

Embodiment 24

The method according to embodiment 1, wherein the aqueous suspensioncomprising microfibrillated cellulose and inorganic particulate materialwith enhanced viscosity and tensile strength properties obtained by themethod is suitable for use in a method of making paper or coating paper,paints and coatings, inks, oilfield chemicals, composites, consumerproducts, cosmetic products, pharmacological products and food products.

Embodiment 25

The method according to embodiment 1, wherein said method furthercomprises one or more of high shear mixing, homogenization and refiningeither before or after the sonication step.

Embodiment 26

A method for preparing an aqueous suspension comprising microfibrillatedcellulose with enhanced viscosity and tensile strength properties, themethod comprising a step of microfibrillating a fibrous substratecomprising cellulose in an aqueous environment to produce an aqueoussuspension comprising microfibrillated cellulose, and further comprisingsubjecting the aqueous suspension comprising microfibrillated celluloseto sonication to produce the aqueous suspension comprisingmicrofibrillated cellulose with enhanced viscosity and tensile strengthproperties.

Embodiment 27

The method according to embodiment 26, wherein said sonication isconducted with one or more devices selected from a group consisting ofan ultrasonic probe, an ultrasonic water bath, an ultrasonichomogenizer, an ultrasonic foil and an ultrasonic horn.

Embodiment 28

The method according to embodiment 26, wherein said tensile strength ofthe aqueous suspension comprising microfibrillated cellulose withenhanced viscosity and tensile strength properties is increased by atleast 5% over the aqueous suspension comprising microfibrillatedcellulose not subject to sonication.

Embodiment 29

The method according to embodiment 26, wherein said tensile strength ofthe aqueous suspension comprising microfibrillated cellulose withenhanced viscosity and tensile strength properties is increased by atleast 10% over the aqueous suspension comprising microfibrillatedcellulose not subject to sonication.

Embodiment 30

The method according to embodiment 26, wherein said tensile strength ofthe aqueous suspension comprising microfibrillated cellulose withenhanced viscosity and tensile strength properties is increased by atleast 20% over the aqueous suspension comprising microfibrillatedcellulose not subject to sonication.

Embodiment 31

The method according to embodiment 26, wherein said aqueous suspensioncomprising microfibrillated cellulose is subject to sonication at anenergy consumption of up to 1000 kwh per tonne of dried fibrils.

Embodiment 32

The method according to embodiment 26, wherein said aqueous suspensioncomprising microfibrillated cellulose is subject to sonication at anenergy consumption of up to 1500 kwh per tonne of dried fibrils.

Embodiment 33

The method according to embodiment 26, wherein said aqueous suspensioncomprising microfibrillated cellulose is subject to sonication at anenergy consumption of up to 2500 kWh per tonne of dried fibrils.

Embodiment 34

The method according to embodiment 26, wherein said sonication is run incontinuous mode.

Embodiment 35

The method according to embodiment 26, wherein said sonication is run inpulse mode.

Embodiment 36

The method according to embodiment 26, wherein said aqueous suspensioncomprising microfibrillated cellulose is formed into semi-dry productprior to sonication.

Embodiment 37

The method according to embodiment 36, wherein said semi-dry product isformed into a belt-pressed cake prior to sonication.

Embodiment 38

The method according to embodiment 26, wherein said viscosity of theaqueous suspension comprising microfibrillated cellulose with enhancedviscosity and tensile strength properties is increased by at least 5%over the aqueous suspension comprising microfibrillated cellulose notsubject to sonication.

Embodiment 39

The method according to embodiment 26, wherein the sonication isperformed at an amplitude of up to 60%.

Embodiment 40

The method according to embodiment 26, wherein the sonication isperformed at an amplitude of up to 80%.

Embodiment 41

The method according to embodiment 26, wherein the sonication isperformed at an amplitude of up to 100%.

Embodiment 42

The method according to embodiment 26, wherein the fibrous substratecomprising cellulose is in the form of a pulp, for example, a chemicalpulp, or a chemithermomechanical pulp, or a mechanical pulp, or arecycled pulp, or a paper broke pulp, or a papermill waste stream, orwaste from a papermill, or combinations thereof.

Embodiment 43

The method according to embodiment 26, wherein the aqueous suspensioncomprising microfibrillated cellulose with enhanced viscosity andtensile strength properties obtained by the method is suitable for usein a method of making paper or coating paper, paints and coatings, inks,oilfield chemicals, composites, consumer products, cosmetic products,pharmacological products and food products.

Embodiment 44

The method according to embodiment 26, wherein said method furthercomprises one or more of high shear mixing, homogenization and refiningeither before or after the sonication step.

Embodiment 45

A method for re-dispersing dewatered, partially dried or essentiallydried microfibrillated cellulose, the method comprising the steps of:

-   -   (a) adding a quantity of a suitable dispersing liquid to a        closed tank, wherein the tank comprises an inlet and an outlet        connected to a pump comprising a first inlet and a first outlet,        and a flow cell comprising a second inlet and a second outlet,        and further comprising at least one sonication probe, thereby        forming a closed recirculation loop;    -   (b) adding a quantity of dewatered, partially dried or        essentially dried microfibrillated cellulose to the tank in        sufficient quantity to yield a liquid composition of        microfibrillated cellulose at a desired solids concentration;    -   wherein the liquid composition comprising microfibrillated        cellulose of step (b) is continuously recirculated through the        recirculation loop;    -   (c) applying ultrasonic energy of at least 200 kWh/t        intermittently or continuously by the sonotrode at a frequency        range of 20 to 100 Hz to the liquid composition of        microfibrillated cellulose,

thereby forming a re-dispersed suspension comprising microfibrillatedcellulose with tensile strength and/or viscosity properties.

Embodiment 46

The method of embodiment 45, wherein the dewatered, partially dried oressentially dried microfibrillated cellulose composition furthercomprises at least one inorganic particulate material.

Embodiment 47

The method of embodiment 45 or 46, wherein the dispersing liquid iswater.

Embodiment 48

The method of embodiment 47, wherein the ultrasonic energy input is fromabout 1,000 kWh/t to 10,000 kWh/t.

Embodiment 49

The method of embodiment 45 or 46, wherein the flow cell has a coolingjacket for maintaining a temperature of the suspension ofmicrofibrillated cellulose in the range of about 1° C. to about 80° C.

Embodiment 50

The method of embodiment 49, wherein the temperature is roomtemperature.

Embodiment 51

The method of embodiment 49, wherein the temperature is 20° C.

Embodiment 52

The method of embodiment 45 or 46, wherein the flow cell comprises anadjustable valve at the second outlet to create back pressure of therecirculated liquid of from about 0 to about 10 bar.

Embodiment 53

The method of embodiment 52, wherein the pressure is 3 bar.

Embodiment 54

The method of embodiment 45 or 46, wherein the flow cell has one or moreboosters to mechanically increase or decrease the amplitude of the atleast one sonotrode.

Embodiment 55

The method of embodiment 45 or 46, wherein the liquid composition ofmicrofibrillated cellulose is about 0.5% to 5% fibre solids.

Embodiment 56

The method of embodiment 55, wherein the liquid composition ofmicrofibrillated cellulose is about 1.5% fibre solids.

Embodiment 57

The method of embodiment 55, wherein the liquid composition ofmicrofibrillated cellulose is about 1.8% fibre solids.

Embodiment 58

The method of embodiment 55, wherein the liquid composition ofmicrofibrillated cellulose is about 2.5% fibre solids.

Embodiment 59

The method of embodiment 45, wherein the microfibrillated cellulose ispelletized.

Embodiment 60

The method of embodiment 46, wherein the microfibrillated cellulosecomposition comprising inorganic particulate material is pelletized.

Embodiment 61

The method of embodiment 45 or 46, wherein the ultrasonic energy wasapplied for about 1 to about 120 minutes.

Embodiment 62

The method of embodiment 61, wherein the ultrasonic energy was appliedfor about 30 minutes.

Embodiment 63

The method of embodiment 45 or 46, wherein the recirculation loopfurther comprises a high shear mixer.

Embodiment 64

The method of embodiment 45 or 46, wherein the suspension ofmicrofibrillated cellulose has an FLT index of 7.5 Nm/g or more.

Embodiment 65

The method of embodiment 45 or 46, wherein the suspension ofmicrofibrillated cellulose has an FLT index of 8.0 Nm/g or more.

Embodiment 66

The method of embodiment 45 or 46, wherein the suspension ofmicrofibrillated cellulose has an FLT index of 8.5 Nm/g or more.

Embodiment 67

The method of embodiment 45 or 46, wherein the suspension ofmicrofibrillated cellulose has an FLT index of 10.0 Nm/g or more.

Embodiment 68

The method of embodiment 45 or 46, wherein the liquid compositioncomprising microfibrillation cellulose is recirculated for about 30 toabout 120 minutes.

Embodiment 69

The method of embodiment 45 or 46, wherein the liquid compositioncomprising microfibrillation cellulose is recirculated for about 30minutes.

Embodiment 70

A re-dispersed microfibrillated cellulose suspension produced by theprocess of embodiment 45 or 46.

We claim:
 1. A method for re-dispersing dewatered, partially dried oressentially dried microfibrillated cellulose, the method comprising thesteps of: (a) adding a quantity of a suitable dispersing liquid to atank having at least a first and a second inlet and an outlet, whereinthe tank further comprises a mixer and a pump attached to the outlet;(b) adding a quantity of dewatered, partially dried or essentially driedmicrofibrillated cellulose to the tank through the first inlet insufficient quantity to yield a liquid composition of microfibrillatedcellulose at a desired solids concentration of 0.5 to 5% fibre solids;(c) mixing the dispersing liquid and the dewatered, partially dried oressentially dried microfibrillated cellulose in the tank with the mixerto partially de-agglomerate and re-disperse the microfibrillatedcellulose to form a flowable slurry; (d) pumping the flowable slurrywith the pump to an inlet of a flow cell, wherein the flow cellcomprises a recirculation loop and one or more sonication probe inseries and at least a first and a second outlet, wherein the secondoutlet of the flow cell is connected to the second inlet of the tank,thereby providing for a continuous recirculation loop providing for thecontinuous application of ultrasonic energy to the slurry for a desiredtime period and/or total energy, wherein the flow cell comprises anadjustable valve at the second outlet to create back pressure of therecirculated slurry, further wherein the liquid composition comprisingmicrofibrillated cellulose of step (c) is continuously recirculatedthrough the recirculation loop at an operating pressure of 0 to 4 barand at a temperature of 20° C. to 50° C.; (e) applying an ultrasonicenergy input to the slurry of 200 to 10,000 kWh/t continuously by thesonication probe at a frequency range of 19 to 100 kHz and at anamplitude of up to 100% to the physical limitations of the sonicatorused for 1 to 120 minutes; (f) collecting the re-dispersed slurrycomprising microfibrillated cellulose with enhanced tensile strengthand/or viscosity properties from the first outlet of the flow cell in asuitable holding vessel.
 2. The method of claim 1, wherein thedewatered, partially dried or essentially dried microfibrillatedcellulose composition further comprises at least one inorganicparticulate material.
 3. The method of claim 2, wherein the dispersingliquid is water.
 4. The method of claim 1, wherein the dispersing liquidis water.
 5. The method of claim 4, wherein the ultrasonic energy isapplied until a cumulative ultrasonic energy input of 2,500 kWh/tisachieved.
 6. The method of claim 1, wherein the ultrasonic energy inputis from about 1,000 kWh/t to about 2,000 kWh/t.
 7. The method of claim2, wherein the ultrasonic energy input is from about 1,000 kWh/t toabout 2,000 kWh/t.
 8. The method of claim 1, wherein the ultrasonicenergy input is from about 200 kWh/t to about 400 kWh/t.
 9. The methodof claim 2, wherein the ultrasonic energy input is from about 200 kWh/tto about 400 kWh/t.
 10. The method of claim 1, wherein the flow cell hasa cooling jacket for maintaining a temperature of the suspension ofmicrofibrillated cellulose in the range of about 20° C. to about 50° C.11. The method of claim 2, wherein the flow cell has a cooling jacketfor maintaining a temperature of the suspension of microfibrillatedcellulose in the range of about 20° C. to about 50° C.
 12. The method ofclaim 1, wherein the temperature is room temperature.
 13. The method ofclaim 2, wherein the temperature is room temperature.
 14. The method ofclaim 1, wherein the temperature is 20° C.
 15. The method of claim 2,wherein the temperature is 20° C.
 16. The method of claim 1, wherein theback pressure of the recirculated liquid is 3 bar.
 17. The method ofclaim 2, wherein the back pressure of the recirculated liquid is 3 bar.18. The method of claim 1, wherein the flow cell further comprises oneor more boosters to mechanically increase or decrease the amplitude ofthe at least one sonication probe.
 19. The method of claim 2, whereinthe flow cell further comprises one or more boosters to mechanicallyincrease or decrease the amplitude of the at least one sonication probe.20. The method of claim 1, wherein the liquid composition ofmicrofibrillated cellulose is about 0.5% to about 1%.
 21. The method ofclaim 2, wherein the liquid composition of microfibrillated cellulose isabout 0.5% to about 1%.
 22. The method of claim 1, wherein the liquidcomposition of microfibrillated cellulose is about 1.5% fibre solids.23. The method of claim 2, wherein the liquid composition ofmicrofibrillated cellulose is about 1.5% fibre solids.
 24. The method ofclaim 1, wherein the liquid composition of microfibrillated cellulose isabout 1.8% fibre solids.
 25. The method of claim 2, wherein the liquidcomposition of microfibrillated cellulose is about 1.8% fibre solids.26. The method of claim 1, wherein the liquid composition ofmicrofibrillated cellulose is about 2.5% fibre solids.
 27. The method ofclaim 2, wherein the liquid composition of microfibrillated cellulose isabout 2.5% fibre solids.
 28. The method of claim 1, wherein the liquidcomposition of microfibrillated cellulose is about 2.5% fibre solids.29. The method of claim 2, wherein the liquid composition ofmicrofibrillated cellulose is about 2.5% fibre solids.
 30. The method ofclaim 1, wherein the microfibrillated cellulose is pelletized.
 31. Themethod of claim 2 wherein the microfibrillated cellulose compositioncomprising inorganic particulate material is pelletized.
 32. The methodof claim 1, wherein the ultrasonic energy is applied for about 30minutes.
 33. The method of claim 2, wherein the ultrasonic energy isapplied for about 30 minutes.
 34. The method of claim 1, wherein theultrasonic energy is applied until a specified ultrasonic energy inputis achieved greater than 200 kWh/t.
 35. The method of claim 2, whereinthe ultrasonic energy is applied until a specified ultrasonic energyinput is achieved greater than 200 kWh/t.
 36. The method of claim 1,wherein the ultrasonic energy is applied until a specified cumulativeultrasonic energy input greater than 400 kWh/t is achieved.
 37. Themethod of claim 2, wherein the ultrasonic energy is applied until aspecified cumulative energy input greater than 400 kWh/t is achieved.38. The method of claim 1, wherein the ultrasonic energy is applieduntil a cumulative ultrasonic energy input of 500 kWh/tis achieved. 39.The method of claim 2, wherein the ultrasonic energy is applied until acumulative ultrasonic energy input of 500 kWh/tis achieved.
 40. Themethod of claim 1, wherein the ultrasonic energy is applied until acumulative ultrasonic energy input of 1,000 kWh/t is achieved.
 41. Themethod of claim 2, wherein the ultrasonic energy is applied until acumulative ultrasonic energy input of 1,000 kWh/t is achieved.
 42. Themethod of claim 1, wherein the ultrasonic energy is applied until acumulative ultrasonic energy input of 1,500 kWh/t is achieved.
 43. Themethod of claim 2, wherein the ultrasonic energy is applied until a 15cumulative ultrasonic energy input of 1,500 kWh/tis achieved.
 44. Themethod of claim 1, wherein the ultrasonic energy is applied until acumulative ultrasonic energy input of 2,000 kWh/t is achieved.
 45. Themethod of claim 2, wherein the ultrasonic energy is applied until acumulative ultrasonic energy input of 2,000 kWh/t is achieved.
 46. Themethod of claim 1, wherein the recirculation loop further comprises ahigh shear mixer.
 47. The method of claim 2, wherein the recirculationloop further comprises a high shear mixer.
 48. The method of claim 1,wherein the liquid composition comprising microfibrillation cellulose isrecirculated for about 30 to about 120 minutes.
 49. The method of claim48, wherein the liquid composition comprising microfibrillationcellulose is recirculated for about 30 minutes.
 50. The method of claim2, wherein the liquid composition comprising microfibrillation celluloseis recirculated for about 30 to about 120 minutes.
 51. The method ofclaim 50, wherein the liquid composition comprising microfibrillationcellulose is recirculated for about 30 minutes.
 52. The method of claim1, wherein sonication is run in pulse mode.
 53. The method of claim 2,wherein sonication is run in pulse mode.
 54. The method of claim 1,wherein said partially dry product is formed into a belt-pressed cakeprior to sonication.
 55. The method of claim 2, wherein said partiallydry product is formed into a belt-pressed cake prior to sonication. 56.The method of claim 1, wherein the microfibrillated cellulose may beprepared from chemical pulp, or a chemithermomechanical pulp, or amechanical pulp, or a recycled pulp, or a paper broke pulp, or apapermill waste stream, or waste from a papermill, or combinationsthereof.
 57. The method of claim 2, wherein the microfibrillatedcellulose may be prepared from chemical pulp, or a chemithermomechanicalpulp, or a mechanical pulp, or a recycled pulp, or a paper broke pulp,or a papermill waste stream, or waste from a papermill, or combinationsthereof.
 58. The method of claim 2, wherein the inorganic particulatematerial is selected from the group consisting of: an alkaline earthmetal carbonate or sulphate, a hydrous kandite clay, an anhydrous(calcined) kandite clay, talc, mica, perlite or diatomaceous earth, orcombinations thereof.
 59. The method of claim 2, wherein the inorganicparticulate material is selected from the group consisting of: calciumcarbonate, magnesium carbonate, dolomite, gypsum, kaolin, halloysite,ball clay, metakaolin, fully calcined kaolin, or combinations thereof.60. The method of claim 2, wherein the inorganic particulate material iscalcium carbonate.
 61. The method of claim 2, wherein the inorganicparticulate material is kaolin.
 62. The method of claim 2, wherein theinorganic particulate material is a combination of calcium carbonate andkaolin.
 63. The method of claim 1, wherein the aqueous suspensioncomprising microfibrillated cellulose with enhanced viscosity andtensile strength properties obtained by the method is suitable for usein a method of making paper or coating paper, paints and coatings, inks,oilfield chemicals, composites, consumer products, cosmetic products,pharmacological products and food products.
 64. The method of claim 2,wherein the aqueous suspension comprising microfibrillated cellulose andinorganic particulate material with enhanced viscosity and tensilestrength properties obtained by the method is suitable for use in amethod of making paper or coating paper, paints and coatings, inks,oilfield chemicals, composites, consumer products, cosmetic products,pharmacological products and food products.
 65. The method of claim 1,wherein said method further comprises one or more of high shear mixing,homogenization and refining either before or after the sonication step.66. The method of claim 2, wherein said method further comprises one ormore of high shear mixing, homogenization and refining either before orafter the sonication step.